Polyorganosilsesquioxane, hard coat film, adhesive sheet, and laminate

ABSTRACT

Provided is a polyorganosilsesquioxane capable of forming, when cured, a cured product that offers high surface hardness and good heat resistance, is highly flexible, and has excellent processability. The present invention relates to a polyorganosilsesquioxane including a constitutional unit represented by Formula (1). The polyorganosilsesquioxane includes a constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of 5 or more. The polyorganosilsesquioxane has a total proportion of the constitutional unit represented by Formula (1) and a constitutional unit represented by Formula (4) of 55% to 100% by mole based on the total amount (100% by mole) of all siloxane constitutional units. The polyorganosilsesquioxane has a number-average molecular weight of 1000 to 3000 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.0 to 3.0.[R1SiO3/2]  (1)[Chem. 2][RaSiO3/2]  (I)[Chem. 3][RbSiO(ORc)]  (II)[Chem. 4][R1SiO(ORc)]  (4)

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of copending U.S. application Ser. No.16/000,313, filed on Jun. 5, 2018, which is a Divisional of U.S.application Ser. No. 15/100,733, filed on Jun. 1, 2016, which is aNational Phase of PCT International Application No. PCT/JP2014/080832 onNov. 14, 2014, which claims the benefit under 35 U.S.C. § 119(a) toPatent Application No. 2014-179898, filed in Japan on Sep. 4, 2014,Patent Application No. 2014-084592, filed in Japan on Apr. 16, 2014,Patent Application No. 2014-034689, filed in Japan on Feb. 25, 2014, andPatent Application No. 2013-257900, filed in Japan on Dec. 13, 2013, allof which are hereby expressly incorporated by reference into the presentapplication.

TECHNICAL FIELD

The present invention relates to a polyorganosilsesquioxane, to acurable composition containing the polyorganosilsesquioxane, and to acured product of the curable composition. The present invention alsorelates to a hard coat film including a hard coat layer derived from ahard-coating composition (hard-coating agent) containing thepolyorganosilsesquioxane. The present invention further relates to acomposition (adhesive composition) containing thepolyorganosilsesquioxane and to an adhesive sheet and a laminate eachprepared using the composition.

BACKGROUND ART

Some conventionally distributed hard coat films include a substrate and,on one or both sides of the substrate, a hard coat layer that has apencil hardness of about 3H on a surface thereof. The hard coat layer inthe hard coat films is mainly formed from a material selected fromUV-curable acrylic monomers (e.g., see Patent Literature (PTL) 1). Forhigher pencil hardness of the hard coat layer surface, some hard coatfilms further contain nanoparticles in the hard coat layer.

In contrast, glass is known as a material having extremely high surfacehardness. Among such glass, there is known glass that has been subjectedto an alkali ion exchange treatment and has a higher surface pencilhardness of up to 9H. However, due to its poor flexibility andprocessability, such glass cannot be subjected to production andprocessing in a roll form by a roll-to-roll process, but is required tobe produced and processed in a sheet form. This leads to high productioncost.

CITATION LIST Patent Literature

PTL 1: Japanese Unexamined Patent Application Publication (JP-A) No.2009-279840

SUMMARY OF INVENTION Technical Problem

However, the hard coat films prepared using the UV-curable acrylicmonomers are not yet considered to have sufficient surface hardness. Ingeneral, as possible solutions to offer higher hardness, amultifunctional UV-curable acrylic monomer is used and/or the hard coatlayer is formed to be thick. Disadvantageously, however, these solutionscause the hard coat layer to undergo larger cure shrinkage andconsequently cause the hard coat film to suffer from curling and/orcracking. Assume that the hard coat layer further containsnanoparticles. Unfortunately in this case, the nanoparticles aggregateto cause the hard coat layer to haze, when the nanoparticles have poorcompatibility with the UV-curable acrylic monomer.

In contrast, the alkali ion exchange treatment of the glassdisadvantageously yields a large amount of alkaline wastewater and putsa heavy load on the environment. Further disadvantageously, such glassis heavy and fragile and leads to high cost. Under these circumstances,demands have been made to provide organic materials that offerflexibility and processability at excellent levels and have high surfacehardness.

In addition, recently, such hard coat films have been applied onto awider and wider range of uses. This demands that the hard coat layers ofthe hard coat films have high surface hardness as described above and,in particular, have excellent heat resistance. However, the hard coatlayers in the hard coat films prepared using the UV-curable acrylicmonomers are considered to be insufficient also from the viewpoint ofheat resistance.

Accordingly, the present invention has an object to provide apolyorganosilsesquioxane capable of forming, when cured, a cured productthat offers high surface hardness and good heat resistance, is highlyflexible, and has excellent processability.

The present invention has another object to provide a hard coat filmthat is still flexible and is producible and processable by aroll-to-roll process even while sustaining high surface hardness andgood heat resistance.

The present invention has yet another object to provide the hard coatfilm that is processable by punching.

The present invention has still another object to provide an adhesivecomposition (adhesive) capable of forming a cured product (adhesivemember) that has high heat resistance and is highly flexible; and anadhesive sheet and a laminate each prepared using the adhesivecomposition (adhesive).

Solution to Problem

The inventors of the present invention found a polyorganosilsesquioxanethat includes an epoxy-containing silsesquioxane constitutional unit(unit structure), has proportions or ratios of specific structures (aratio of a T3 unit to a T2 unit, and the proportion of theepoxy-containing silsesquioxane constitutional unit) each controlledwithin specific ranges, and has a number-average molecular weight and amolecular-weight dispersity controlled within specific ranges. Theinventors found that a curable composition containing thepolyorganosilsesquioxane, when cured, forms a cured product that offershigh surface hardness and good heat resistance, is highly flexible, andhas excellent processability. The inventors also found a hard coat filmincluding a hard coat layer derived from a hard-coating compositioncontaining the polyorganosilsesquioxane and found that this hard coatfilm is still flexible and is producible and processable by aroll-to-roll process even while sustaining high surface hardness andgood heat resistance. In addition, the inventors found that a curablecomposition containing the polyorganosilsesquioxane is advantageouslyusable as an adhesive composition (adhesive) that forms a cured product(adhesive member) having high heat resistance and being highly flexible.The present invention has been made based on these findings.

Specifically, the present invention provides, in one aspect, apolyorganosilsesquioxane including a constitutional unit represented byFormula (1):[Chem. 1][R¹SiO_(3/2)]  (1)wherein R¹ represents an epoxy-containing group. Thepolyorganosilsesquioxane includes a constitutional unit represented byFormula (I) and a constitutional unit represented by Formula (II) in amole ratio of the constitutional unit represented by Formula (I) to theconstitutional unit represented by Formula (II) of 5 or more. Formulae(I) and (II) are expressed as follows:[Chem. 2][R^(a)SiO_(3/2)]  (I)where R^(a) is selected from an epoxy-containing group, a substituted orunsubstituted aryl group, a substituted or unsubstituted aralkyl group,a substituted or unsubstituted cycloalkyl group, a substituted orunsubstituted alkyl group, a substituted or unsubstituted alkenyl group,and a hydrogen atom,[Chem. 3][R^(b)SiO(OR^(c))]  (II)where R^(b) is selected from an epoxy-containing group, a substituted orunsubstituted aryl group, a substituted or unsubstituted aralkyl group,a substituted or unsubstituted cycloalkyl group, a substituted orunsubstituted alkyl group, a substituted or unsubstituted alkenyl group,and a hydrogen atom; and R^(c) is selected from a hydrogen atom and aC₁-C₄ alkyl group. The polyorganosilsesquioxane has a total proportionof the constitutional unit represented by Formula (1) and aconstitutional unit represented by Formula (4) of 55% to 100% by molebased on the total amount (100% by mole) of all siloxane constitutionalunits. Formula (4) is expressed as follows:[Chem. 4][R¹SiO(OR^(c))]  (4)where R¹ is as defined in Formula (1); and R^(c) is as defined inFormula (II). The polyorganosilsesquioxane has a number-averagemolecular weight of 1000 to 3000 and a molecular-weight dispersity(weight-average molecular weight to number-average molecular weightratio) of 1.0 to 3.0.

The polyorganosilsesquioxane may further include a constitutional unitrepresented by Formula (2):[Chem. 5][R²SiO_(3/2)]  (2)where R² is selected from a substituted or unsubstituted aryl group, asubstituted or unsubstituted aralkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkylgroup, and a substituted or unsubstituted alkenyl group.

In the polyorganosilsesquioxane, R¹ may be selected from a grouprepresented by Formula (1a), a group represented by Formula (1b), agroup represented by Formula (1c), and a group represented by Formula(1d). Formulae (1a), (1b), (1c), and (1c) are expressed as follows:

where R^(1a) represents a straight or branched chain alkylene group,

where R^(1b) represents a straight or branched chain alkylene group,

where R^(1c) represents a straight or branched chain alkylene group,

where R^(1d) represents a straight or branched chain alkylene group.

In the polyorganosilsesquioxane, R² is preferably a substituted orunsubstituted aryl group.

The present invention provides, in another aspect, a curable compositioncontaining the polyorganosilsesquioxane.

The curable composition may further contain a curing catalyst.

The curing catalyst in the curable composition may be a cationicphotoinitiator.

The curing catalyst in the curable composition may be a cationic thermalinitiator.

The curable composition may further contain a vinyl ether compound.

The vinyl ether compound in the curable composition may include a vinylether compound containing a hydroxy group in the molecule.

The curable composition may be a curable composition for the formationof a hard coat layer.

The curable composition may also be an adhesive composition.

The present invention provides, in yet another aspect, a cured productof the curable composition.

In still another aspect, the present invention provides a hard coat filmthat includes a substrate, and a hard coat layer disposed on or over atleast one side of the substrate. The hard coat layer is a layer of acured product of the curable composition.

The hard coat layer in the hard coat film may have a thickness of 1 to200 μm.

The hard coat film may be producible by a roll-to-roll process.

The hard coat film may further include a surface-protecting film on asurface of the hard coat layer.

The present invention provides, in another aspect, a method forproducing a hard coat film. The method includes Step A, Step B, and StepC. In Step A, a wound (rolled) substrate is unwound. In Step B, thecurable composition is applied onto at least one side of the unwoundsubstrate, and the applied curable composition is cured to form a hardcoat layer on the substrate to thereby give a hard coating film. In StepC, the resulting hard coating film is rewound into a roll. Steps A, B,and C are successively performed.

In another aspect, the present invention provides an adhesive sheet thatincludes a substrate, and an adhesive layer disposed on or over thesubstrate. The adhesive layer is a layer of the curable composition.

In addition and advantageously, the present invention provide a laminateincluding three or more layers. The three or more layers include twoadherend layers, and an adhesive layer between the two adherend layers.The adhesive layer is a layer of a cured product of the curablecomposition.

Advantageous Effects of Invention

The polyorganosilsesquioxane according to the present invention has theconfiguration. Assume that the polyorganosilsesquioxane is incorporatedas an essential component into a curable composition, and the curablecomposition is cured. The curable composition in this case forms a curedproduct that offers high surface hardness and good heat resistance, ishighly flexible, and has excellent processability. The hard coat filmaccording to the present invention has the configuration, is thereforestill flexible and is producible and processable by a roll-to-rollprocess even while sustaining high surface hardness and good heatresistance. The hard coat film according to the present invention istherefore excellent both in quality and cost. The curable compositioncontaining the polyorganosilsesquioxane according to the presentinvention as an essential component is also advantageously usable as anadhesive composition (adhesive) that forms a cured product (adhesivemember) having high heat resistance and being highly flexible. The useof the adhesive composition gives an adhesive sheet and a laminate.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a photomicrograph (at 100-fold magnification) of ends of ahard coat film prepared in Example 20, which is a sample after punching.

DESCRIPTION OF EMBODIMENTS

Polyorganosilsesquioxane

The polyorganosilsesquioxane (silsesquioxane) according to the presentinvention includes a constitutional unit represented by Formula (1). Thepolyorganosilsesquioxane includes a constitutional unit represented byFormula (I) and a constitutional unit represented by Formula (II) in amole ratio of the constitutional unit represented by Formula (I) to theconstitutional unit represented by Formula (II) of 5 or more. Theconstitutional unit represented by Formula (I) is also referred to as a“T3 unit”. The constitutional unit represented by Formula (II) is alsoreferred to as a “T2 unit”. The mole ratio of the constitutional unitrepresented by Formula (I) to the constitutional unit represented byFormula (II) is also referred to as a “T3 to T2 ratio”. Thepolyorganosilsesquioxane has a total proportion of the constitutionalunit represented by Formula (1) and an after-mentioned constitutionalunit represented by Formula (4) of 55% to 100% by mole based on thetotal amount (100% by mole) of all siloxane constitutional units. Thepolyorganosilsesquioxane has a number-average molecular weight of 1000to 3000 and a molecular-weight dispersity of 1.0 to 3.0, where themolecular-weight dispersity is the ratio of the weight-average molecularweight to the number-average molecular weight. Formulae (1), (I), and(II) are expressed as follows:[Chem. 10][R¹SiO_(3/2)]  (1)[Chem. 11][R^(a)SiO_(3/2)]  (I)[Chem. 12][R^(b)SiO(OR^(c))]  (II)

The constitutional unit represented by Formula (1) is a silsesquioxaneconstitutional unit (so-called T unit) generally represented by theformula: RSiO_(3/2). R in the formula is selected from a hydrogen atomand a monovalent organic group. This definition is also applied to thefollowing description. The constitutional unit represented by Formula(1) is derived from a corresponding hydrolyzable trifunctional silanecompound via hydrolysis and condensation reaction. The correspondinghydrolyzable trifunctional silane compound is exemplified by, but is notlimited to, after-mentioned compounds represented by Formula (a).

In Formula (1), R¹ represents an epoxy-containing group (monovalentgroup). Specifically, the polyorganosilsesquioxane according to thepresent invention is a cationically curable compound (cationicallypolymerizable compound) that contains an epoxy group in the molecule.The epoxy-containing group may be selected from, but is not limited to,known or common groups containing an oxirane ring. Among them, preferredare groups represented by Formula (1a), groups represented by Formula(1b), groups represented by Formula (1c), and groups represented byFormula (1d); of which the groups represented by Formula (1a) and thegroups represented by Formula (1) are preferred, and the groupsrepresented by Formula (1a) are more preferred. These are preferred fromthe viewpoints of curability of the curable composition, and surfacehardness and heat resistance of the cured product. Formulae (1a), (1b),(1c), and (1d) are expressed as follows:

In Formula (1a), R^(1a) represents a straight or branched chain alkylenegroup. Examples of the straight or branched chain alkylene groupinclude, but are not limited to, C₁-C₁₀ straight or branched chainalkylene groups such as methylene, methylmethylene, dimethylmethylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,hexamethylene, and decamethylene groups. In particular, Ria ispreferably selected from C₁-C₄ straight chain alkylene groups and C₃ andC₄ branched chain alkylene groups, more preferably selected fromethylene, trimethylene, and propylene groups, and furthermore preferablyselected from ethylene and trimethylene groups. These are preferred fromthe viewpoints of surface hardness and curability of the cured product.

In Formula (1b), R^(1b) represents a straight or branched chain alkylenegroup and is exemplified by groups as with Ria. In particular, R^(1b) ispreferably selected from C₁-C₄ straight chain alkylene groups and C₃ andC₄ branched chain alkylene groups, more preferably selected fromethylene, trimethylene, and propylene groups, and furthermore preferablyselected from ethylene and trimethylene groups. These are preferred fromthe viewpoints of surface hardness and curability of the cured product.

In Formula (1c), R^(1c) represents a straight or branched chain alkylenegroup, and is exemplified by groups as with R^(1a). In particular,R^(1c) is preferably selected from C₁-C₄ straight chain alkylene groupsand C₃ and C₄ branched chain alkylene groups, more preferably selectedfrom ethylene, trimethylene, and propylene groups, and furthermorepreferably selected from ethylene and trimethylene groups. These arepreferred from the viewpoints of surface hardness and curability of thecured product.

In Formula (1d), R^(1d) represents a straight or branched chain alkylenegroup, and is exemplified by groups as with Ria. In particular, R^(1d)is preferably selected from C₁-C₄ straight chain alkylene groups and C₃and C₄ branched chain alkylene groups, more preferably selected fromethylene, trimethylene, and propylene groups, and furthermore preferablyselected from ethylene and trimethylene groups. These are preferred fromthe viewpoints of surface hardness and curability of the cured product.

In particular, R¹ in Formula (1) is preferably selected from the groupsrepresented by Formula (1a) in which R^(1a) is ethylene group, and ismore preferably 2-(3′,4′-epoxycyclohexyl)ethyl group.

The polyorganosilsesquioxane according to the present invention mayinclude one type of the constitutional unit represented by Formula (1)alone or may include two or more different constitutional unitsrepresented by Formula (1).

In addition to the constitutional unit represented by Formula (1), thesilsesquioxane constitutional unit (RSiO_(3/2)) in thepolyorganosilsesquioxane according to the present invention may furtherinclude a constitutional unit represented by Formula (2):[Chem. 17][R²SiO_(3/2)]  (2)

The constitutional unit represented by Formula (2) is a silsesquioxaneconstitutional unit (T unit) generally represented by the formula:RSiO_(3/2). Specifically, the constitutional unit represented by Formula(2) is derived from a corresponding hydrolyzable trifunctional silanecompound via hydrolysis and condensation reaction. The hydrolyzabletrifunctional silane compound is exemplified by, but is not limited to,after-mentioned compounds represented by Formula (b).

In Formula (2), R² is selected from a substituted or unsubstituted arylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkylgroup, and a substituted or unsubstituted alkenyl group. Non-limitingexamples of the aryl group include phenyl, tolyl, and naphthyl groups.Non-limiting examples of the aralkyl group include benzyl and phenethylgroups. Non-limiting examples of the cycloalkyl group includecyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkylgroup include, but are not limited to, straight or branched chain alkylgroups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl,s-butyl, t-butyl, and isopentyl groups. Examples of the alkenyl groupinclude, but are not limited to, straight or branched chain alkenylgroups such as vinyl, allyl, and isopropenyl groups.

The substituted aryl, substituted aralkyl, substituted cycloalkyl,substituted alkyl, and substituted alkenyl groups are exemplified by,but are not limited to, groups respectively corresponding to the aryl,aralkyl, cycloalkyl, alkyl, and alkenyl groups, except with part or allof hydrogen atoms or backbone skeleton of the corresponding compoundbeing substituted with at least one selected from the group consistingof ether group, ester group, carbonyl group, siloxane group, halogenatoms (e.g., fluorine atom), acrylic group, methacrylic group, mercaptogroup, amino group, and hydroxy group.

In particular, R² is preferably selected from substituted orunsubstituted aryl groups, substituted or unsubstituted alkyl groups,and substituted or unsubstituted alkenyl groups, is more preferablyselected from substituted or unsubstituted aryl groups, and isfurthermore preferably phenyl group.

The proportions of the silsesquioxane constitutional units (theconstitutional unit represented by Formula (1) and the constitutionalunit represented by Formula (2)) in the polyorganosilsesquioxaneaccording to the present invention can be adjusted as appropriate by thecomposition (formulation) of starting materials (hydrolyzabletrifunctional silanes) to form these constitutional units.

The polyorganosilsesquioxane according to the present invention mayfurther include, other than the constitutional unit represented byFormula (1) and the constitutional unit represented by Formula (2), atleast one siloxane constitutional unit selected from the groupconsisting of silsesquioxane constitutional units (RSiO_(3/2)) excludingthe constitutional unit represented by Formula (1) and theconstitutional unit represented by Formula (2); constitutional unitsrepresented by the formula: R₃SiO_(1/2) (so-called M units);constitutional units represented by the formula: R²SiO (so-called Dunits); and constitutional units represented by the formula SiO₂(so-called Q units). A non-limiting example of the silsesquioxaneconstitutional units excluding the constitutional unit represented byFormula (1) and the constitutional unit represented by Formula (2)includes a constitutional unit represented by Formula (3):[Chem. 18][HSiO_(3/2)]  (3)

The polyorganosilsesquioxane according to the present invention includesa constitutional unit represented by Formula (I) and a constitutionalunit represented by Formula (II) in a T3 to T2 ratio of theconstitutional unit represented by Formula (I) (T3 unit) to theconstitutional unit represented by Formula (II) (T2 unit) of 5 or more,as described above. The T3 to T2 ratio is preferably 5 to 18, morepreferably 6 to 16, and furthermore preferably 7 to 14. Thepolyorganosilsesquioxane, as having a T3 to T2 ratio of 5 or more,contributes to significantly higher surface hardness and adhesiveness ofthe cured product and the hard coat layer.

The constitutional unit represented by Formula (I) is more specificallyrepresented by Formula (I′) below. The constitutional unit representedby Formula (II) is more specifically represented by Formula (II′) below.The three oxygen atoms bonded to the silicon atom specified in thestructure represented by Formula (I′) are bonded respectively to othersilicon atoms (silicon atoms not shown in Formula (I′)). In contrast,the two oxygen atoms respectively positioned above and below the siliconatom specified in the structure represented by Formula (II′) are bondedrespectively to other silicon atoms (silicon atoms not shown in Formula(II′)). Specifically, the T3 unit and the T2 unit are constitutionalunits (T units) derived from corresponding hydrolyzable trifunctionalsilane compounds via hydrolysis and condensation reaction. Formulae (I′)and (II′) are expressed as follows:

R^(a) in Formula (I) (as with R^(a) in Formula (I′)) and R^(b) inFormula (II) (as with R^(b) in Formula (II′)) are each independentlyselected from an epoxy-containing group, a substituted or unsubstitutedaryl group, a substituted or unsubstituted aralkyl group, a substitutedor unsubstituted cycloalkyl group, a substituted or unsubstituted alkylgroup, a substituted or unsubstituted alkenyl group, and a hydrogenatom. Examples of R^(a) and R^(b) are as with R¹ in Formula (1) and R²in Formula (2). R^(a) in Formula (I) and R^(b) in Formula (II) areindependently derived from groups (groups excluding alkoxy groups andhalogen atoms) bonded to silicon atom(s) in hydrolyzable trifunctionalsilane compounds used as starting materials to form thepolyorganosilsesquioxane according to the present invention. Examples ofthe groups (excluding alkoxy groups and halogen atoms) bonded to thesilicon atoms include, but are not limited to, R¹, R², and hydrogen atomin after-mentioned Formulae (a), (b), and (c).

R^(c) in Formula (II) (as with R^(c) in Formula (II′)) is selected froma hydrogen atom and a C₁-C₄ alkyl group. Non-limiting examples of theC₁-C₄ alkyl group include C₁-C₄ straight or branched chain alkyl groupssuch as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups. Ingeneral, the alkyl group as R^(c) in Formula (II) is derived from analkoxy group in the hydrolyzable silane compound used as a startingmaterial to form the polyorganosilsesquioxane according to the presentinvention. The alkoxy group herein is exemplified by after-mentionedalkoxy groups as X¹ to X³.

The T3 to T2 ratio in the polyorganosilsesquioxane according to thepresent invention may be determined typically by ²⁹Si-NMR spectrummeasurement. In the ²⁹Si-NMR spectrum, the silicon atom in theconstitutional unit (T3 unit) represented by Formula (I) and the siliconatom in the constitutional unit (T2 unit) represented by Formula (II)offer signals (peaks) at different positions (different chemicalshifts). The integral ratio between these peaks are calculated todetermine the T3 to T2 ratio. Specifically, for example, assume that thepolyorganosilsesquioxane according to the present invention includes aconstitutional unit represented by Formula (1) in which R¹ is a2-(3′,4′-epoxycyclohexyl)ethyl group. In this case, the silicon atom inthe structure (T3 unit) represented by Formula (I) offers a signalappearing at −64 to −70 ppm, the silicon atom in the structure (T2 unit)represented by Formula (II) offers a signal appearing at −54 to −60 ppm.In this case, the integral ratio of the signal appearing at −64 to −70ppm (assigned to the T3 unit) to the signal appearing at −54 to −60 ppm(assigned to the T2 unit) is calculated to determine the T3 to T2 ratio.

The ²⁹Si-NMR spectrum of the polyorganosilsesquioxane according to thepresent invention may be determined typically with an apparatus underconditions as follows.

Measuring apparatus: trade name JNM-ECA500 NMR (supplied by JEOL Ltd.)

Solvent: deuterated chloroform

Number of scans: 1800

Measurement temperature: 25° C.

The fact that the polyorganosilsesquioxane according to the presentinvention has a T3 to T2 ratio of 5 or more means that thepolyorganosilsesquioxane according to the present invention includesboth the T3 unit and the T2 unit and includes the T2 unit in an amountat a specific level or higher relative to the T3 unit. Non-limitingexamples of the T2 unit include constitutional units represented byFormula (4), constitutional units represented by Formula (5), andconstitutional units represented by Formula (6). R¹ in Formula (4) andR² in Formula (5) are respectively as with R¹ in Formula (1) and R² inFormula (2). R^(c) in Formulae (4) to (6) is, independently in eachoccurrence, selected from a hydrogen atom and a C₁-C₄ alkyl group, aswith R^(c) in Formula (II). Formula (4), (5), and (6) are expressed asfollows:[Chem. 21][R¹SiO(OR^(c))]  (4)[Chem. 22][R²SiO(OR^(c))]  (5)[Chem. 23][HSiO(OR^(c))]  (6)

In general, a silsesquioxane of complete cage structure is apolyorganosilsesquioxane that includes T3 unit(s) alone and is devoid ofT2 units in the molecule. Specifically, assume that thepolyorganosilsesquioxane according to the present invention, which has aT3 to T2 ratio of 5 or more and has a number-average molecular weight of1000 to 3000 and a molecular-weight dispersity of 1.0 to 3.0, has oneintrinsic absorption peak occurring at about 1100 cm⁻¹ in an FT-IRspectrum as mentioned below. This polyorganosilsesquioxane is indicatedto have an incomplete cage silsesquioxane structure.

The presence of a cage (incomplete cage) silsesquioxane structure in thepolyorganosilsesquioxane according to the present invention is verifiedby that the polyorganosilsesquioxane according to the present inventionis approximately devoid of intrinsic absorption peaks at about 1050 cm⁻¹and at about 1150 cm⁻¹, but offers one intrinsic absorption peak atabout 1100 cm⁻¹ in an FT-IR spectrum (reference: R. H. Raney, M. Itoh,A. Sakakibara, and T. Suzuki, Chem. Rev. 95, 1409 (1995)). In contrast,a polyorganosilsesquioxane having intrinsic absorption peaks at about1050 cm⁻¹ and at about 1150 cm⁻¹ in an FT-IR spectrum is generallyidentified as one having a ladder-like silsesquioxane structure. TheFT-IR spectrum of the polyorganosilsesquioxane according to the presentinvention may be measured typically with an apparatus under conditionsas follows.

Measuring apparatus: trade name FT-720 (supplied by HORIBA, Ltd.)

Measurement method: through transmission

Resolution: 4 cm⁻¹

Measurement wavenumber range: 400 to 4000 cm⁻¹

Number of scans: 16

The total proportion (total amount) of the constitutional unitrepresented by Formula (1) and the constitutional unit represented byFormula (4) is 55% to 100% by mole as described above, and is preferably65% to 100% by mole, and furthermore preferably 80% to 99% by mole,based on the total amount (100% by mole) of siloxane constitutionalunits (all siloxane constitutional units; total amount of M units, Dunits, T units, and Q units) in the polyorganosilsesquioxane accordingto the present invention. The polyorganosilsesquioxane, as including thetwo constitutional units in a total proportion of 55% by mole or more,allows the curable composition to have better curability and allows thecured product to have significantly higher surface hardness andadhesiveness. The proportions of the individual siloxane constitutionalunits in the polyorganosilsesquioxane according to the present inventionmay be calculated typically based on the composition (formulation) ofstarting materials, and/or by NMR spectrometry.

The total proportion (total amount) of the constitutional unitrepresented by Formula (2) and the constitutional unit represented byFormula (5) is not limited, but is preferably 0% to 70% by mole, morepreferably 0% to 60% by mole, furthermore preferably 0% to 40% by mole,and particularly preferably 1% to 15% by mole, based on the total amount(100% by mole) of siloxane constitutional units (all siloxaneconstitutional units; total amount of M units, D units, T units, and Qunits) in the polyorganosilsesquioxane according to the presentinvention. The polyorganosilsesquioxane, when having a total proportionof the two constitutional units of 70% by mole or less, has a relativelylarger total proportion of the constitutional unit represented byFormula (1) and constitutional unit represented by Formula (4). Thistends to allow the curable composition to have better curability andtends to allow the cured product to have surface hardness andadhesiveness at still higher levels. In contrast, thepolyorganosilsesquioxane, when having a total proportion of the twoconstitutional units of 1% by mole or more, tends to contribute tobetter gas barrier properties of the cured product.

The total proportion (total amount) of the constitutional unitrepresented by Formula (1), the constitutional unit represented byFormula (2), the constitutional unit represented by Formula (4), and theconstitutional unit represented by Formula (5) is not limited, but ispreferably 60% to 100% by mole, more preferably 70% to 100% by mole, andfurthermore preferably 80% to 100% by mole, based on the total amount(100% by mole) of siloxane constitutional units (all siloxaneconstitutional units; total amount of M units, D units, T units, and Qunits) in the polyorganosilsesquioxane according to the presentinvention. The polyorganosilsesquioxane, when having a total proportionof the constitutional units of 60% by mole or more, tends to allow thecured product to have surface hardness and adhesiveness at still higherlevels.

The polyorganosilsesquioxane according to the present invention has anumber-average molecular weight (Mn) of 1000 to 3000 as described above,and preferably 1000 to 2800, and more preferably 1100 to 2600, asdetermined by gel permeation chromatography and calibrated with apolystyrene standard. The polyorganosilsesquioxane, as having anumber-average molecular weight of 1000 or more, allows the curedproduct to have heat resistance, scratch resistance, and adhesiveness atstill higher levels. In contrast, the polyorganosilsesquioxane, ashaving a number-average molecular weight of 3000 or less, has bettercompatibility with other components in the curable composition, and thisallows the cured product to have still better heat resistance.

The polyorganosilsesquioxane according to the present invention has amolecular-weight dispersity (Mw/Mn) of 1.0 to 3.0 as described above,and preferably 1.1 to 2.0, and more preferably 1.2 to 1.9, as determinedby gel permeation chromatography and calibrated with a polystyrenestandard. The polyorganosilsesquioxane, as having a molecular-weightdispersity of 3.0 or less, allows the cured product to have surfacehardness and adhesiveness at still higher levels. In contrast, thepolyorganosilsesquioxane, as having a molecular-weight dispersity of 1.1or more, tends to be readily present as a liquid and to have betterhandleability.

The number-average molecular weight and the molecular-weight dispersityof the polyorganosilsesquioxane according to the present invention maybe measured typically with an apparatus under conditions as follows.

Measuring apparatus: trade name LC-20AD (supplied by ShimadzuCorporation)

Columns: two Shodex KF-801 columns, one KF-802 column, and one KF-803column (supplied by Showa Denko K.K.)

Measurement temperature: 40° C.

Eluent: THF, at a sample concentration of 0.1% to 0.2% by weight

Flow rate: 1 mL/min.

Detector: UV-VIS Detector (trade name SPD-20A, supplied by ShimadzuCorporation)

Molecular weight: calibrated with a polystyrene standard

The polyorganosilsesquioxane according to the present invention may havea 5% weight loss temperature (T_(d5)) not limited, but of preferably330° C. or higher (e.g., 330° C. to 450° C.), more preferably 340° C. orhigher, and furthermore preferably 350° C. or higher, in an airatmosphere. The polyorganosilsesquioxane, when having a 5% weight losstemperature of 330° C. or higher, tends to allow the cured product tohave still better heat resistance. In particular, the 5% weight losstemperature of the polyorganosilsesquioxane according to the presentinvention may be controlled to 330° C. or higher as thepolyorganosilsesquioxane has a T3 to T2 ratio of 5 or more, has anumber-average molecular weight of 1000 to 3000 and a molecular-weightdispersity of 1.0 to 3.0, and offers one intrinsic peak at about 1100cm⁻¹ in the FT-IR spectrum. The 5% weight loss temperature refers to atemperature at which a sample heated at a constant rate of temperaturerise loses 5% of its weight as compared with one before heating. The 5%weight loss temperature serves as an index for heat resistance. The 5%weight loss temperature may be measured by thermogravimetry (TGA) in anair atmosphere at a rate of temperature rise of 5° C./min.

The polyorganosilsesquioxane according to the present invention isproducible by any of known or common polysiloxane production methodswithout limitation, but may be produced typically by subjecting one ormore hydrolyzable silane compounds to hydrolysis and condensation.However, the hydrolyzable silane compound(s) essentially includes ahydrolyzable trifunctional silane compound (compound represented byFormula (a)) to form the above-mentioned constitutional unit representedby Formula (1).

More specifically, for example, the polyorganosilsesquioxane accordingto the present invention may be produced by subjecting the compoundrepresented by Formula (a), and, as needed, a compound represented byFormula (b) and/or a compound represented by Formula (c) to hydrolysisand condensation. The compound represented by Formula (a), (b) or (c) isa hydrolyzable silane compound to form the silsesquioxane constitutionalunit (T unit) in the polyorganosilsesquioxane according to the presentinvention. Formulae (a), (b), and (c) are expressed as follows:[Chem. 24]R¹Si(X¹)₃  (a)[Chem. 25]R²Si(X²)₃  (b)[Chem. 26]HSi(X³)₃  (c)

The compound represented by Formula (a) is a compound that forms theconstitutional unit represented by Formula (1) in thepolyorganosilsesquioxane according to the present invention. R¹ inFormula (a) represents an epoxy-containing group, as with R¹ in Formula(1). Specifically, R¹ in Formula (a) is preferably selected from thegroups represented by Formula (1a), the groups represented by Formula(1b), the groups represented by Formula (1c), and the groups representedby Formula (1d); more preferably selected from the groups represented byFormula (1a) and the groups represented by Formula (1c); furthermorepreferably selected from the groups represented by Formula (1a);particularly preferably selected from the groups represented by Formula(1a) in which Ria is an ethylene group; and is especially preferably2-(3′,4′-epoxycyclohexyl)ethyl group.

X¹ in Formula (a) is, independently in each occurrence, selected from analkoxy group and a halogen atom. Non-limiting examples of the alkoxygroup as X¹ include C₁-C₄ alkoxy groups such as methoxy, ethoxy,propoxy, isopropyloxy, butoxy, and isobutyloxy groups. Non-limitingexamples of the halogen atom as X¹ include fluorine, chlorine, bromine,and iodine atoms. In particular, X¹ is, independently in eachoccurrence, preferably selected from alkoxy groups and is morepreferably selected from methoxy and ethoxy groups. The threeoccurrences of X¹ may be identical to or different from one another

The compound represented by Formula (b) is a compound that forms theconstitutional unit represented by Formula (2) in thepolyorganosilsesquioxane according to the present invention. R² inFormula (b) is selected from a substituted or unsubstituted aryl group,a substituted or unsubstituted aralkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkylgroup, and a substituted or unsubstituted alkenyl group, as with R² inFormula (2). Specifically, R² in Formula (b) is, independently in eachoccurrence, preferably selected from substituted or unsubstituted arylgroups, substituted or unsubstituted alkyl groups, and substituted orunsubstituted alkenyl groups; is more preferably selected fromsubstituted or unsubstituted aryl groups; and is furthermore preferablyphenyl group.

X² in Formula (b) is selected from an alkoxy group and a halogen atom.Non-limiting examples of X² include those exemplified as X¹. Inparticular, X² is, independently in each occurrence, preferably selectedfrom alkoxy groups and is more preferably selected from methoxy andethoxy groups. The three occurrences of X² may be identical to ordifferent from one another

The compound represented by Formula (c) is a compound that forms theconstitutional unit represented by Formula (3) in thepolyorganosilsesquioxane according to the present invention. X³ inFormula (c) is selected from an alkoxy group and a halogen atom.Non-limiting examples of X³ include those exemplified as X¹. Inparticular, X³ is, independently in each occurrence, preferably selectedfrom alkoxy groups and is more preferably selected from methoxy andethoxy groups. The three occurrences of X³ may be identical to ordifferent from one another

The hydrolyzable silane compounds for use herein may further include oneor more hydrolyzable silane compounds other than the compoundsrepresented by Formulae (a) to (c). Non-limiting examples of the otherhydrolyzable silane compounds include hydrolyzable trifunctional silanecompounds excluding the compounds represented by Formula (a) to (c);hydrolyzable monofunctional silane compounds, which form M units;hydrolyzable bifunctional silane compounds, which form D units; andhydrolyzable tetrafunctional silane compounds, which form Q units.

The amount and formulation of hydrolyzable silane compound(s) to be usedmay be adjusted as appropriate according to a desired structure of thepolyorganosilsesquioxane according to the present invention. Forexample, the amount of the compound represented by Formula (a) is notlimited, but is preferably 55% to 100% by mole, more preferably 65% to100% by mole, and furthermore preferably 80% to 99% by mole, based onthe total amount (100% by mole) of the hydrolyzable silane compound(s)to be used.

The amount of the compound represented by Formula (b) is not limited,but is preferably 0% to 70% by mole, more preferably 0% to 60% by mole,furthermore preferably 0% to 40% by mole, and particularly preferably 1%to 15% by mole, based on the total amount (100% by mole) of hydrolyzablesilane compound(s) to be used.

The total proportion of the compound represented by Formula (a) and thecompound represented by Formula (b) is not limited, but is preferably60% to 100% by mole, more preferably 70% to 100% by mole, andfurthermore preferably 80% to 100% by mole, based on the total amount(100% by mole) of the hydrolyzable silane compound(s) to be used.

Assume that the hydrolyzable silane compound(s) to be used includes twoor more different compounds. In this case, the hydrolysis andcondensation reactions of these hydrolyzable silane compounds may beperformed simultaneously or successively. The reactions, when performedsuccessively, may be performed in any order.

The hydrolysis and condensation reaction(s) of the hydrolyzable silanecompound(s) may be performed in the presence of, or in the absence of, asolvent. In particular, the reaction(s) is preferably performed in thepresence of a solvent. Examples of the solvent include, but are notlimited to, aromatic hydrocarbons such as benzene, toluene, xylenes, andethylbenzene; ethers such as diethyl ether, dimethoxyethane,tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethylketone, and methyl isobutyl ketone; esters such as methyl acetate, ethylacetate, isopropyl acetate, and butyl acetate; amides such asN,N-dimethylformamide and N,N-dimethylacetamide; nitriles such asacetonitrile, propionitrile, and benzonitrile; and alcohols such asmethanol, ethanol, isopropyl alcohol, and butanol. Among them, thesolvent is preferably selected from ketones and ethers. Each ofdifferent solvents may be used alone or in combination.

The amount of the solvent is not limited, and may be adjusted asappropriate according typically to a desired reaction time, within therange of 0 to 2000 parts by weight per 100 parts by weight of the totalamount of the hydrolyzable silane compound(s).

The hydrolysis and condensation reaction(s) of the hydrolyzable silanecompound(s) is preferably performed in the presence of a catalyst andwater. The catalyst may be either an acid catalyst or an alkalinecatalyst. Non-limiting examples of the acid catalyst include mineralacids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoricacid, and boric acid; phosphoric esters; carboxylic acids such as aceticacid, formic acid, and trifluoroacetic acid; sulfonic acids such asmethanesulfonic acid, trifluoromethanesulfonic acid, andp-toluenesulfonic acid; solid acids such as activated clay; and Lewisacids such as iron chloride. Non-limiting examples of the alkalinecatalyst include alkali metal hydroxides such as lithium hydroxide,sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkalineearth metal hydroxides such as magnesium hydroxide, calcium hydroxide,and barium hydroxide; alkali metal carbonates such as lithium carbonate,sodium carbonate, potassium carbonate, and cesium carbonate; alkalineearth metal carbonates such as magnesium carbonate; alkali metalhydrogencarbonates such as lithium hydrogencarbonate, sodiumhydrogencarbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, and cesium hydrogencarbonate; alkali metal organicacid salts (e.g., acetates), such as lithium acetate, sodium acetate,potassium acetate, and cesium acetate; alkaline earth metal organic acidsalts (e.g., acetates), such as magnesium acetate; alkali metalalkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide,sodium isopropoxide, potassium ethoxide, and potassium t-butoxide;alkali metal phenoxides such as sodium phenoxide; amines such astriethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene,and 1,5-diazabicyclo[4.3.0]non-5-ene, of which tertiary amines aretypified; and nitrogen-containing heteroaromatic compounds such aspyridine, 2,2′-bipyridyl, and 1,10-phenanthroline. Each of differentcatalysts may be used alone or in combination. The catalyst may be usedin the form of a solution or dispersion typically in water or a solvent.

The amount of the catalyst is not limited and may be adjusted asappropriate within the range of 0.002 to 0.200 mole per mole of all thehydrolyzable silane compound(s).

The amount of water in the hydrolysis and condensation reaction is notlimited and may be adjusted as appropriate within the range of 0.5 to 20mol per mole of all the hydrolyzable silane compound(s).

The water may be added in any manner not limited. The water may be addedat once as a whole quantity (total amount to be used), or may be addedsuccessively. The water, when added successively, may be addedcontinuously or intermittently.

It is important that the hydrolysis and condensation reaction of thehydrolyzable silane compound(s) is performed, in particular, under suchreaction conditions that the resulting polyorganosilsesquioxaneaccording to the present invention has a T3 to T2 ratio of 5 or more.The hydrolysis and condensation reaction may be performed at a reactiontemperature not limited, but of preferably 40° C. to 100° C., and morepreferably 45° C. to 80° C. The reaction, when performed at a reactiontemperature controlled within the range, tends to more efficiently allowthe polyorganosilsesquioxane to have a T3 to T2 ratio of 5 or more. Thehydrolysis and condensation reaction may be performed for a reactiontime not limited, but of preferably 0.1 to 10 hours, and more preferably1.5 to 8 hours. The hydrolysis and condensation reaction may beperformed under normal atmospheric pressure, under pressure (under aload) or under reduced pressure. The atmosphere in which the hydrolysisand condensation reaction is performed is not limited and may be any ofan atmosphere of an inert gas, such as nitrogen atmosphere or argonatmosphere; and an atmosphere in the presence of oxygen, such as airatmosphere. The reaction is, however, preferably performed in anatmosphere of an inert gas.

The hydrolysis and condensation reaction of the hydrolyzable silanecompound(s) yields the polyorganosilsesquioxane according to the presentinvention. After the completion of the hydrolysis and condensationreaction, the catalyst is preferably neutralized so as to restrain epoxygroup ring-opening. The polyorganosilsesquioxane according to thepresent invention may be separated/purified typically by a separationmeans such as water washing, acid washing, alkali washing, filtration,concentration, distillation, extraction, crystallization,recrystallization, or column chromatography, or a separation means asany combination of them.

The polyorganosilsesquioxane according to the present invention has theconfiguration. Assume that the polyorganosilsesquioxane is incorporatedas an essential component into a curable composition. The resultingcurable composition forms, when cured, a cured product that offers highsurface hardness and good heat resistance, is highly flexible, and hasexcellent processability. The curable composition also forms a curedproduct that has excellent adhesiveness.

Curable Composition

The curable composition according to the present invention is a curablecomposition (curable resin composition) that contains thepolyorganosilsesquioxane according to the present invention as anessential component. As will be described later, the curable compositionaccording to the present invention may further contain one or morecomponents such as a curing catalyst (in particular, a cationicphotoinitiator), a surface control agent, and a surface modifier.

The curable composition according to the present invention may containeach of different polyorganosilsesquioxanes according to the presentinvention alone or in combination.

The curable composition according to the present invention may containthe polyorganosilsesquioxane(s) according to the present invention in acontent (blending amount) not limited, but of preferably from 70% byweight to less than 100% by weight, more preferably 80% to 99.8% byweight, and furthermore preferably 90% to 99.5% by weight, based on thetotal amount (100% by weight) of the curable composition excluding thesolvent. The curable composition, when containing thepolyorganosilsesquioxane(s) according to the present invention in acontent of 70% by weight or more, tends to allow the cured product tohave surface hardness and adhesiveness at still higher levels. Incontrast, the curable composition, when containing thepolyorganosilsesquioxane(s) according to the present invention in acontent of less than 100% by weight, can contain a curing catalyst. Thistends to more efficiently promote the curing of the curable composition.

The curable composition according to the present invention may containthe polyorganosilsesquioxane(s) according to the present invention in aproportion not limited, but of preferably 70% to 100% by weight, morepreferably 75% to 98% by weight, and furthermore preferably 80% to 95%by weight, based on the total amount (100% by weight) of allcationically curable compounds contained in the curable composition. Thecurable composition, when containing the polyorganosilsesquioxane(s)according to the present invention in a content of 70% by weight ormore, tends to allow the cured product to have surface hardness andadhesiveness at still higher levels.

The curable composition according to the present invention preferablyfurther contains a curing catalyst. Among such curing catalysts, thecurable composition particularly preferably contains a cationicphotoinitiator as the curing catalyst. This is preferred for a shortercuring time for the cured product to become tack-free.

The curing catalyst is a compound that initiates and/or promotes acationic polymerization reaction of cationically curable compounds suchas the polyorganosilsesquioxanes according to the present invention.Non-limiting examples of the curing catalyst include polymerizationinitiators such as cationic photoinitiators (a photoacid generators) andcationic thermal initiators (thermal acid generators).

The cationic photoinitiators may be selected from known or commoncationic photoinitiators and are exemplified by, but are not limited to,sulfonium salts (salts between a sulfonium ion and an anion), iodoniumsalts (salts between an iodonium ion and an anion), selenium salts(salts between a selenium ion and an anion), ammonium salts (saltsbetween an ammonium ion and an anion), phosphonium salts (salts betweena phosphonium ion and an anion), and salts between a transition metalcomplex ion and an anion. The curable composition may contain each ofdifferent cationic photoinitiators alone or in combination.

Examples of the sulfonium salts include, but are not limited to,triarylsulfonium salts such as the trade name HS-1PC (supplied bySan-Apro Ltd.), the trade name LW-S1 (supplied by San-Apro Ltd.),triphenylsulfonium salts, tri-p-tolylsulfonium salts,tri-o-tolylsulfonium salts, tris(4-methoxyphenyl)sulfonium salts,1-naphthyl(diphenyl)sulfonium salts, 2-naphthyl(diphenyl)sulfoniumsalts, tris(4-fluorophenyl)sulfonium salts, tri-1-naphthylsulfoniumsalts, tri-2-naphthylsulfonium salts, tris(4-hydroxyphenyl)sulfoniumsalts, diphenyl[4-(phenylthio)phenyl]sulfonium salts, and4-(p-tolylthio)phenyl(di-(p-phenyl))sulfonium salts; diarylsulfoniumsalts such as diphenyl(phenacyl)sulfonium salts,diphenyl(4-nitrophenacyl)sulfonium salts, diphenyl(benzyl)sulfoniumsalts, and diphenyl(methyl)sulfonium salts; monoarylsulfonium salts suchas phenyl(methyl)benzylsulfonium salts,4-hydroxyphenyl(methyl)benzylsulfonium salts, and4-methoxyphenyl(methyl)benzylsulfonium salts; and trialkylsulfoniumsalts such as dimethyl(phenacyl)sulfonium salts,phenacyltetrahydrothiophenium salts, and dimethyl(benzyl)sulfoniumsalts.

Non-limiting examples of the diphenyl[4-(phenylthio)phenyl]sulfoniumsalts include commercial products available typically under the tradename CPI-101A (supplied by San-Apro Ltd.,diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, as a 50%propylene carbonate solution), and the trade name CPI-100P (supplied bySan-Apro Ltd., diphenyl[4-(phenylthio)phenyl]sulfoniumhexafluorophosphate, as a 50% propylene carbonate solution).Non-limiting examples of the triarylsulfonium salts also includecommercial products typically under the trade name K1-S (supplied bySan-Apro Ltd., an antimony-free (non-antimony) triarylsulfonium salt).

Non-limiting examples of the iodonium salts include the trade nameUV9380C (supplied by Momentive Performance Materials Japan LLC,bis(4-dodecylphenyl)iodonium hexafluoroantimonate, as a 45% alkylglycidyl ether solution), the trade name RHODORSIL PHOTOINITIATOR 2074(supplied by Rhodia Japan, Ltd.,[(1-methylethyl)phenyl](methylphenyl)iodoniumtetrakis(pentafluorophenyl)borate), the trade name WPI-124 (supplied byWako Pure Chemical Industries, Ltd.), diphenyliodonium salts,di-p-tolyliodonium salts, bis(4-dodecylphenyl)iodonium salts, andbis(4-methoxyphenyl)iodonium salts.

Examples of the selenium salts include, but are not limited to,triarylselenium salts such as triphenylselenium salts,tri-p-tolylselenium salts, tri-o-tolylselenium salts,tris(4-methoxyphenyl)selenium salts, and 1-naphthyl(diphenyl)seleniumsalts; diarylselenium salts such as diphenyl(phenacyl)selenium salts,diphenyl(benzyl)selenium salts, and diphenyl(methyl)selenium salts;monoarylselenium salts such as phenyl(methyl)benzylselenium salts; andtrialkylselenium salts such as dimethyl(phenacyl)selenium salts.

Examples of the ammonium salts include, but are not limited to,tetraalkylammonium salts such as tetramethylammonium salts,ethyl(trimethyl)ammonium salts, diethyl(dimethyl)ammonium salts,triethyl(methyl)ammonium salts, tetraethylammonium salts,trimethyl(n-propyl)ammonium salts, and trimethyl(n-butyl)ammonium salts;pyrrolidium salts such as N,N-dimethylpyrrolidium salts andN-ethyl-N-methylpyrrolidium salts; imidazolinium salts such asN,N′-dimethylimidazolinium salts and N,N′-diethylimidazolinium salts;tetrahydropyrimidium salts such as N,N′-dimethyltetrahydropyrimidiumsalts and N,N′-diethyltetrahydropyrimidium salts; morpholinium saltssuch as N,N-dimethylmorpholinium salts and N,N-diethylmorpholiniumsalts; piperidinium salts such as N,N-dimethylpiperidinium salts andN,N-diethylpiperidinium salts; pyridinium salts such asN-methylpyridinium salts and N-ethylpyridinium salts; imidazolium saltssuch as N,N′-dimethylimidazolium salts; quinolium salts such asN-methylquinolium salts; isoquinolium salts such as N-methylisoquinoliumsalts; thiazonium salts such as benzylbenzothiazonium salts; andacridium salts such as benzylacridium salts.

Non-limiting examples of the phosphonium salts includetetraarylphosphonium salts such as tetraphenylphosphonium salts,tetra-p-tolylphosphonium salts, and tetrakis(2-methoxyphenyl)phosphoniumsalts; triarylphosphonium salts such as triphenyl(benzyl)phosphoniumsalts; and tetraalkylphosphonium salts such astriethyl(benzyl)phosphonium salts, tributyl(benzyl)phosphonium salts,tetraethylphosphonium salts, tetrabutylphosphonium salts, andtriethyl(phenacyl)phosphonium salts.

Non-limiting examples of the transition metal complex ion salts includesalts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Cr⁺ and (η5-cyclopentadienyl) (η6-xylene)Cr⁺; and salts ofiron complex cations such as (η5-cyclopentadienyl) (η6-toluene)Fe⁺ and(η5-cyclopentadienyl) (η6-xylene) Fe⁺.

Non-limiting examples of the anions constituting the salts include SbF₆⁻, PF₆ ⁻, BF₄ ⁻, (CF₃CF₂)₃PF₃ ⁻, (CF₃CF₂CF₂)₃PF₃ ⁻, (C₆F₅)₄B⁻,(C₆F₅)₄Ga⁻, sulfonate anions (e.g., trifluoromethanesulfonate anion,pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion,methanesulfonate anion, benzenesulfonate anion, and p-toluenesulfonateanion), (CF₃SO₂)₃C⁻, (CF₃SO₂)₂N⁻, perhalogenate ions, halogenatedsulfonate ions, sulfate ions, carbonate ion, aluminate ions,hexafluorobismuthate ions, carboxylate ions, arylborate ions,thiocyanate ions, and nitrate ions.

Examples of the cationic thermal initiators include, but are not limitedto, arylsulfonium salts, aryliodonium salts, allene-ion complexes,quaternary ammonium salts, aluminum chelates, and borontrifluoride-amine complexes.

Non-limiting examples of the arylsulfonium salts includehexafluoroantimonate salts. The curable composition according to thepresent invention may employ any of commercial products typically underthe trade names SP-66 and SP-77 (each supplied by ADEKA CORPORATION);and the trade names San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, andSan-Aid SI-150L (each supplied by SANSHIN CHEMICAL INDUSTRY CO., LTD.).Non-limiting examples of the aluminum chelates include, but are notlimited to, aluminum ethyl acetoacetate diisopropylate and aluminumtris(ethyl acetoacetate). Examples of the boron trifluoride aminecomplexes include, but are not limited to, boron trifluoridemonoethylamine complex, boron trifluoride imidazole complex, and borontrifluoride piperidine complex.

The curable composition according to the present invention may containeach of different curing catalysts alone or in combination.

The curable composition according to the present invention may containthe curing catalyst in a content (blending amount) not limited, but ofpreferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0parts by weight, and furthermore preferably 0.1 to 1.0 part by weight(e.g., 0.3 to 1.0 part by weight), per 100 parts by weight of thepolyorganosilsesquioxane according to the present invention. The curablecomposition, when containing the curing catalyst in a content of 0.01part by weight or more, tends to undergo an efficiently sufficientlyproceeding curing reaction and to allow the cured product to havesurface hardness and adhesiveness at still higher levels. In contrast,the curable composition, when containing the curing catalyst in acontent of 3.0 parts by weight or less, tends to have still betterstorage stability and/or to allow the cured product to resist coloring.

The curable composition according to the present invention may furthercontain one or more other cationically curable compounds. The “othercationically curable compounds” refer to cationically curable compoundsexcluding the polyorganosilsesquioxanes according to the presentinvention. The other cationically curable compounds may be selected fromknown or common cationically curable compounds and are exemplified by,but are not limited to, other epoxides, oxetane compounds, and vinylether compounds, where the “other epoxides” refer to epoxides excludingthe polyorganosilsesquioxanes according to the present invention. Thecurable composition according to the present invention may contain eachof different other cationically curable compounds alone or incombination.

The other epoxides may be selected from known or common compoundscontaining at least one epoxy group (oxirane ring) per molecule and areexemplified by, but are not limited to, cycloaliphatic epoxides(cycloaliphatic epoxy resins), aromatic epoxides (aromatic epoxyresins), and aliphatic epoxides (aliphatic epoxy resins).

The cycloaliphatic epoxides may be selected from known or commoncompounds containing at least one alicycle and at least one epoxy groupper molecule and are exemplified by, but are not limited to, (1)compounds containing at least one cycloaliphatic epoxy group permolecule, where the “cycloaliphatic epoxy group” refers to an epoxygroup containing one oxygen atom bonded in triangular arrangement toadjacent two carbon atoms constituting an alicycle; (2) compoundscontaining at least one epoxy group bonded directly via a single bond toan alicycle; and (3) glycidyl ether epoxides that are compoundscontaining at least one alicycle and at least one glycidyl ether groupper molecule.

Non-limiting examples of the compounds (1) containing at least onecycloaliphatic epoxy group per molecule include compounds represented byFormula (i):

In Formula (i), Y is selected from a single bond and a linkage group,where the “linkage group” refers to a divalent group containing at leastone atom. Examples of the linkage group include, but are not limited to,divalent hydrocarbon groups; alkenylene groups, except with part or allof carbon-carbon double bond(s) being epoxidized; carbonyl group; etherbond; ester bond; carbonate group; amide group; and groups eachincluding two or more of these groups bonded to each other.

Non-limiting examples of the divalent hydrocarbon groups include C₁-C₁₈straight or branched chain alkylene groups and divalent alicyclichydrocarbon groups. Examples of the C₁-C₁₈ straight or branched chainalkylene groups include, but are not limited to, methylene,methylmethylene, dimethylmethylene, ethylene, propylene, andtrimethylene groups. Examples of the divalent alicyclic hydrocarbongroups include, but are not limited to, divalent cycloalkylene groups(including cycloalkylidene groups) such as 1,2-cyclopentylene,1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene,1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups.

The alkenylene groups with part or all of carbon-carbon double bond(s)being epoxidized are hereinafter also referred to as “epoxidizedalkenylene groups”. Non-limiting examples of the alkenylene groups inthe epoxidized alkenylene groups include C₂-C₈ straight or branchedchain alkenylene groups such as vinylene, propenylene, 1-butenylene,2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, andoctenylene groups. In particular, of the epoxidized alkenylene groups,preferred are alkenylene groups with all of carbon-carbon double bond(s)being epoxidized, and more preferred are C₂-C₄ alkenylene groups withall of carbon-carbon double bond(s) being epoxidized.

Representative, but non-limiting examples of the cycloaliphatic epoxidesrepresented by Formula (i) include 3,4,3′,4′-diepoxybicyclohexane; andcompounds represented by Formulae (i-1) to (i-10). In Formulae (i-5) and(i-7), 1 and m each independently represent an integer of 1 to 30. R′ inFormula (i-5) represents, independently in each occurrence, a C₁-C₈alkylene group and is preferably a C₁-C₃ straight or branched chainalkylene group such as methylene, ethylene, propylene, or isopropylenegroup. In Formulae (i-9) and (i-10), n1 to n6 each independentlyrepresent an integer of 1 to 30. Non-limiting examples of thecycloaliphatic epoxides represented by Formula (i) also include2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, andbis(3,4-epoxycyclohexylmethyl) ether.

Non-limiting examples of the compounds (2) containing an epoxy groupdirectly bonded via a single bond to an alicycle include compoundsrepresented by Formula (ii):

In Formula (ii), R″ represents a group (p-valent organic group)corresponding to a p-hydric alcohol, except for removing hydroxy group(—OH) in the number of p from the structural formula of the alcohol; andp and n each independently represent a natural number. Non-limitingexamples of the p-hydric alcohol (R″(OH)_(p)) include polyhydricalcohols such as 2,2-bis(hydroxymethyl)-1-butanol, of which C₁-C₁₅alcohols are typified. The number p is preferably 1 to 6, and n ispreferably 1 to 30. When p is 2 or more, the occurrences of n for thegroups present in the respective brackets (outer brackets) may beidentical or different. Examples of the compounds represented by Formula(ii) include, but are not limited to, a1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of2,2-bis(hydroxymethyl)-1-butanol, such as a product under the trade nameEHPE3150 (supplied by Daicel Corporation).

Non-limiting examples of the compounds (3) containing at least onealicycle and at least one glycidyl ether group per molecule includeglycidyl ethers of alicyclic alcohols (in particular, of alicyclicpolyhydric alcohols). More specifically, non-limiting examples of thecompound (3) include hydrogenated bisphenol-A epoxides such as2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane, where thehydrogenated bisphenol-A epoxides are compounds derived from bisphenol-Aepoxides via hydrogenation; hydrogenated bisphenol-F epoxides such asbis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane,bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane,bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, andbis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, where thehydrogenated bisphenol-F epoxides are compounds derived from bisphenol-Fepoxides via hydrogenation; hydrogenated biphenol epoxides; hydrogenatedphenol novolac epoxides; hydrogenated cresol novolac epoxides;hydrogenated cresol novolac epoxides derived from bisphenol-A;hydrogenated naphthalene epoxides; hydrogenated products of epoxidesderived from trisphenolmethane; and hydrogenated epoxides derived fromafter-mentioned aromatic epoxides.

Examples of the aromatic epoxides include, but are not limited to,epi-bis glycidyl ether epoxy resins; high-molecular-weight epi-bisglycidyl ether epoxy resins; novolac-alkyl glycidyl ether epoxy resins;and fluorene-derived epoxides. The epi-bis glycidyl ether epoxy resinsare each obtained by a condensation reaction between a bisphenol andepihalohydrin. Non-limiting examples of the bisphenol includebisphenol-A, bisphenol-F, bisphenol-S, and fluorene-bisphenol. Thehigh-molecular-weight epi-bis glycidyl ether epoxy resins are obtainedby further subjecting the epi-bis glycidyl ether epoxy resins to anaddition reaction with the bisphenol. The novolac-alkyl glycidyl etherepoxy resins are each obtained by subjecting a phenol and an aldehyde toa condensation reaction to give a polyhydric alcohol, and furthersubjecting the polyhydric alcohol to a condensation reaction withepihalohydrin. Non-limiting examples of the phenol include phenol,cresol, xylenol, resorcinol, catechol, bisphenol-A, bisphenol-F, andbisphenol-S. Non-limiting examples of the aldehyde include formaldehyde,acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and salicylaldehyde.The fluorene-derived epoxides each include a fluorene ring, and twophenol skeletons bonded to the 9-position of the fluorene ring, in whichthe hydroxy groups of these phenol skeleton lose hydrogen atoms toexpose oxygen atoms, and glycidyl groups are respectively bondeddirectly or via an alkyleneoxy group to the oxygen atoms.

Examples of the aliphatic epoxides include, but are not limited to,glycidyl ethers of q-hydric alcohols devoid of cyclic structures, whereq represents a natural number; glycidyl esters of monovalent orpolyvalent carboxylic acids such as acetic acid, propionic acid, butyricacid, stearic acid, adipic acid, sebacic acid, maleic acid, and itaconicacid; epoxidized derivatives of double-bond-containing fats and oils,such as epoxidized linseed oil, epoxidized soybean oil, and epoxidizedcastor oil; and epoxidized derivatives of polyolefins (includingpolyalkadienes), such as epoxidized polybutadienes. Non-limitingexamples of the q-hydric alcohols devoid of cyclic structures includemonohydric alcohols such as methanol, ethanol, 1-propyl alcohol,isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, poly(ethylene glycol)s, andpoly(propylene glycol)s; and tri- or higher polyhydric alcohols such asglycerol, diglycerol, erythritol, trimethylolethane, trimethylolpropane,pentaerythritol, dipentaerythritol, and sorbitol. Examples of theq-hydric alcohols also include polyether polyols, polyester polyols,polycarbonate polyols, and polyolefin polyols.

The oxetane compounds may be selected from, but are not limited to,known or common compounds containing at least one oxetane ring permolecule, such as 3,3-bis(vinyloxymethyl)oxetane,3-ethyl-3-(hydroxymethyl)oxetane,3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane,3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane,1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,bis{[1-ethyl(3-oxetanyl)]methyl} ether,4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl,1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene,3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl)}oxetane, xylylenebisoxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane,oxetanylsilsesquioxane, and phenol novolac oxetanes.

The vinyl ether compounds may be selected from known or common compoundscontaining at least one vinyl ether group per molecule and areexemplified by, but are not limited to, 2-hydroxyethyl vinyl ether(ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether,2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether,4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutylvinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinylether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropylvinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinylether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinylether, 1,4-cyclohexanedimethanol divinyl ether,1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanoldivinyl ether, 1,2-cyclohexanedimethanol monovinyl ether,1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinylether, p-xylene glycol divinyl ether, m-xylene glycol monovinyl ether,m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xyleneglycol divinyl ether, ethylene glycol divinyl ether, diethylene glycolmonovinyl ether, diethylene glycol divinyl ether, triethylene glycolmonovinyl ether, triethylene glycol divinyl ether, tetraethylene glycolmonovinyl ether, tetraethylene glycol divinyl ether, pentaethyleneglycol monovinyl ether, pentaethylene glycol divinyl ether,oligoethylene glycol monovinyl ethers, oligoethylene glycol divinylethers, poly(ethylene glycol) monovinyl ethers, poly(ethylene glycol)divinyl ethers, dipropylene glycol monovinyl ether, dipropylene glycoldivinyl ether, tripropylene glycol monovinyl ether, tripropylene glycoldivinyl ether, tetrapropylene glycol monovinyl ether, tetrapropyleneglycol divinyl ether, pentapropylene glycol monovinyl ether,pentapropylene glycol divinyl ether, oligopropylene glycol monovinylethers, oligopropylene glycol divinyl ethers, poly(propylene glycol)monovinyl ethers, poly(propylene glycol) divinyl ethers, isosorbidedivinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butylvinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinylether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether,cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether,trimethylolpropane trivinyl ether, bisphenol-A divinyl ether,bisphenol-F divinyl ether, hydroxyoxanorbornanemethanol divinyl ether,1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether,pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether,and dipentaerythritol hexavinyl ether.

In a preferred embodiment, the curable composition according to thepresent invention further contains a vinyl ether compound as the othercationically curable compound, in addition to thepolyorganosilsesquioxane according to the present invention. Thisconfiguration tends to contribute to still higher surface hardness ofthe cured product. Assume that the curable composition according to thisembodiment of the present invention is cured by irradiation with anactive energy ray (in particular, an ultraviolet ray). In particular inthis case, the curable composition advantageously forms a cured productthat has very high surface hardness with excellent productivity, evenbeing irradiated with the active energy ray at a low irradiance. Forexample, this cured product may be produced without the need for a heattreatment for aging. This allows the cured product and the hard coatfilm to be produced at a higher speed in a production line andcontributes to still better productivity of them.

In an embodiment, the curable composition contains, as the othercationically curable compound, a vinyl ether compound containing atleast one hydroxy group per molecule. Advantageously, the curablecomposition according to this embodiment gives a cured product that hasstill higher surface hardness and offers excellent resistance to thermalyellowing, where the resistance to thermal yellowing is such a propertyas to resist thermal yellowing. This curable composition allows thecured product and the hard coat film to have quality and durability atstill higher levels. The number of hydroxy groups per molecule of thevinyl ether compound containing at least one hydroxy group per moleculeis not limited, but is preferably 1 to 4, and more preferably 1 or 2.Specifically, non-limiting examples of the vinyl ether compoundcontaining at least one hydroxy group per molecule include2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether),3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether,2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether,3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether,3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether,1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinylether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinylether, 1,6-hexanediol monovinyl ether, 1,8-octanediol divinyl ether,1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanolmonovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xyleneglycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycolmonovinyl ether, diethylene glycol monovinyl ether, triethylene glycolmonovinyl ether, tetraethylene glycol monovinyl ether, pentaethyleneglycol monovinyl ether, oligoethylene glycol monovinyl ethers,poly(ethylene glycol) monovinyl ethers, tripropylene glycol monovinylether, tetrapropylene glycol monovinyl ether, pentapropylene glycolmonovinyl ether, oligopropylene glycol monovinyl ethers, poly(propyleneglycol) monovinyl ethers, pentaerythritol trivinyl ether, anddipentaerythritol pentavinyl ether.

The curable composition according to the present invention may containthe other cationically curable compounds in a content (blending amount)not limited, but of preferably 50% by weight or less (e.g., 0% to 50% byweight), more preferably 30% by weight or less (e.g., 0% to 30% byweight), and furthermore preferably 10% by weight or less, relative tothe total amount (100% by weight) of the polyorganosilsesquioxanesaccording to the present invention and the other cationically curablecompounds (total amount of cationically curable compounds). The curablecomposition, when containing the other cationically curable compounds ina content of 50% by weight or less (in particular, 10% by weight orless), tends to allow the cured product to have still better scratchresistance. In contrast, the other cationically curable compounds, whencontained in a content of 10% by weight or more, may impart desiredproperties to the curable composition and/or to the cured product. Suchdesired properties are exemplified by fast curability and adjustedviscosity of the curable composition.

The curable composition according to the present invention may containthe vinyl ether compound (in particular, the vinyl ether compoundcontaining at least one hydroxy group per molecule) in a content(blending amount) not limited, but of preferably 0.01% to 10% by weight,more preferably 0.05% to 9% by weight, and furthermore preferably 1% to8% by weight, relative to the total amount (100% by weight) of thepolyorganosilsesquioxanes according to the present invention and theother cationically curable compounds (total amount of cationicallycurable compounds). The curable composition, when containing the vinylether compound in a content controlled within the range, tends to allowthe cured product to have still higher surface hardness and to have veryhigh surface hardness even when irradiated with an active energy ray(e.g., an ultraviolet ray) at a low irradiance. In particular, thecurable composition, when containing the vinyl ether compound containingat least one hydroxy group per molecule in a content controlled withinthe range, tends to allow the cured product to have particularly highersurface hardness and still better resistance to thermal yellowing.

The curable composition according to the present invention may furthercontain one or more commonly used additives as other optionalcomponents. Non-limiting examples of the additives include fillersincluding inorganic fillers such as precipitated silica, hydrous silica(wet silica), fumed silica, pyrogenic silica, titanium oxide, alumina,glass, quartz, aluminosilicate, iron oxides, zinc oxide, calciumcarbonate, carbon black, silicon carbide, silicon nitride, and boronnitride; inorganic fillers corresponding to these fillers, except forbeing treated with any of organosilicon compounds such asorganohalosilanes, organoalkoxysilanes, and organosilazanes; finepowders of organic resins such as silicone resins, epoxy resins, andfluorocarbon resins; and conductive powders of metals such as silver andcopper. Non-limiting examples of the additives further include curingassistants; solvents such as organic solvents; stabilizers such asantioxidants, ultraviolet absorbers, photostabilizers, thermalstabilizers, and heavy-metal deactivators; flame retardants such asphosphorus flame retardants, halogen flame retardants, and inorganicflame retardants; flame retardant promoters; reinforcing agents such asother fillers; nucleating agents; coupling agents such as silanecoupling agents; lubricants; waxes; plasticizers; release agents; impactmodifiers; color modifiers (hue modifiers); clearing agents; rheologyadjusters such as flow improvers; processability improvers; colorantssuch as dyestuffs and pigments; antistatic agents; dispersing agents;surface control agents such as antifoaming agents, leveling agents, andanti-popping agents; surface modifiers such as slipping agents;delustering agents; antifoaming agents; foam inhibitors; defoamingagents; antimicrobial agents; antiseptic agents (preservatives);viscosity modifiers; thickeners; photosensitizers; and blowing agents.The curable composition may contain each of different additives alone orin combination.

The curable composition according to the present invention may beprepared typically, but not limitatively, by stirring and mixing thecomponents at room temperature or, as needed, with heating. The curablecomposition according to the present invention may be used as a one-partcomposition, or a multi-part composition such as a two-part composition.The one-part composition contains the components, which have beenblended beforehand, and is used as intact. In contrast, in themulti-part composition, two or more parts (portions) of the componentsare stored separately, and the two or more parts are blended inpredetermined proportions before use.

The curable composition according to the present invention ispreferably, but not limitatively, liquid at room temperature (about 25°C.). More specifically, assume that the curable composition according tothe present invention is diluted with a solvent to give a solutioncontaining 20% of the solvent (in particular, assume that the curablecomposition (solution) contains 20% by weight of methyl isobutylketone). In this case, the resulting composition (solution) may have aviscosity of preferably 300 to 20000 mPa·s, more preferably 500 to 10000mPa·s, and furthermore preferably 1000 to 8000 mPa·s at 25° C. Thecurable composition, when having a viscosity as defined above of 300mPa·s or more, tends to allow the cured product to have still betterheat resistance. In contrast, the curable composition, when having aviscosity of 20000 mPa·s or less, tends to be prepared and handled moreeasily and tends to impede remaining of bubbles in the cured product.The viscosity of the curable composition according to the presentinvention is measured with a viscometer (trade name MCR301, supplied byAnton Paar GmbH) at an oscillation angle of a 5%, a frequency of 0.1 to100 (1/s), and a temperature of 25° C.

Cured Product

The curable composition according to the present invention can be curedwhen undergoing progress of a polymerization reaction of cationicallycurable compounds (e.g., the polyorganosilsesquioxane according to thepresent invention) in the curable composition. This gives a curedproduct. The resulting cured product is also referred to as a “curedproduct according to the present invention”. The curing technique may beselected as appropriate from well-known techniques without limitation.For example, curing may be performed by active energy ray irradiationand/or heating. The active energy ray may be any of infrared rays,visible light, ultraviolet rays, X rays, electron beams, alpha rays,beta rays, and gamma rays. Among them, the active energy ray ispreferably an ultraviolet ray for excellent handleability.

Assume that the curable composition according to the present inventionis cured by active energy ray irradiation. Conditions (e.g., activeenergy ray irradiation conditions) in this case are not limited, and areadjustable as appropriate according typically to the type and energy ofthe active energy ray to be applied, and the shape and size of the curedproduct. For example, in the case of ultraviolet ray irradiation, thecurable composition is preferably irradiated typically at about 1 toabout 1000 mJ/cm². The active energy ray irradiation may be performedtypically using any of high-pressure mercury lamps, ultra-high pressuremercury lamps, xenon lamps, carbon arc, metal halide lamps, sunlight,LED lamps, and laser systems. The curing reaction may further proceed byperforming a heat treatment (annealing, aging) after the active energyray irradiation.

In contrast, assume that the curable composition according to thepresent invention is cured by heating. Conditions in this case are notlimited, but the heating (curing) is performed typically preferably at30° C. to 200° C., and more preferably 50° C. to 190° C. The curing timeherein is settable as appropriate.

The curable composition according to the present invention, when cured,forms a cured product that offers high surface hardness and good heatresistance, is highly flexible, and has excellent processability, asdescribed above. Consequently, the curable composition according to thepresent invention is preferably usable, in particular, as a “hard coatlayer-forming curable composition” for the formation of a hard coatlayer in a hard coat film. The hard coat layer-forming curablecomposition is also referred typically as a “hard-coating composition”or a “hard-coating agent”. Assume that the curable composition accordingto the present invention is used as a hard coat layer-forming curablecomposition to form a hard coat layer. In this case, a hard coat filmincluding the resulting hard coat layer maintains high hardness and goodheat resistance, is still flexible, and is producible and processable bya roll-to-roll process.

Hard Coat Film

The hard coat film according to the present invention is a film thatincludes a substrate, and a hard coat layer disposed on or over at leastone side of the substrate. The hard coat layer is a hard coat layerderived from the curable composition (hard coat layer-forming curablecomposition) according to the present invention. Namely, the hard coatlayer is a layer of a cured product of the curable composition accordingto the present invention. The hard coat layer derived from the curablecomposition according to the present invention is herein also referredto as a “hard coat layer according to the present invention”.

The hard coat layer according to the present invention in the hard coatfilm according to the present invention may be disposed on or over onlyone side of, or both sides of the substrate.

The hard coat layer according to the present invention in the hard coatfilm according to the present invention may be disposed partially orentirely on or over at least one side of the substrate.

The “substrate” in the hard coat film according to the present inventionrefers to a portion that serves as a substrate (base) of the hard coatlayer and constitutes another portion than the hard coat layer accordingto the present invention. Non-limiting examples of the substrate includeplastic substrates, metal substrates, ceramic substrates, semiconductorsubstrates, glass substrates, paper substrates, wood substrates (woodensubstrates), surface-coated substrates, and any other known or commonsubstrates. Among them, the substrate is preferably selected fromplastic substrates, which are substrates derived from plastic materials.

Non-limiting examples of the plastic materials constituting the plasticsubstrates include polyesters such as poly(ethylene terephthalate)s(PETs) and poly(ethylene naphthalate)s (PENs); polyimides;polycarbonates; polyamides; polyacetals; poly(phenylene oxide)s;poly(phenylene sulfide)s; polyethersulfones; poly(ether ether ketone)s;cycloolefin polymers including homopolymers (e.g., addition polymers andring-opened polymers) of norbornene monomers, copolymers (e.g., additionpolymers, ring-opened polymer, and any other cyclic olefin copolymers)between norbornene monomers and olefinic monomers, such asnorbornene-ethylene copolymers, and derivatives of them; vinyl polymersincluding poly(methyl methacrylate)s (PMMAs) and any other acrylicresins, polystyrenes, poly(vinyl chloride)s, andacrylonitrile-styrene-butadiene resins (ABS resins); vinylidene polymerssuch as poly(vinylidene chloride)s; cellulosic resins such as triacetylcellulose (TAC); epoxy resins; phenolic resins; melamine resins; urearesins; maleimide resins; silicones; and any other plastic materials.The plastic substrates may include (may be derived from) each ofdifferent plastic materials alone or in combination.

Assume that a hard coat film having excellent transparency is to beobtained as the hard coat film according to the present invention. Inparticular in this case, the plastic substrate for use herein ispreferably selected from substrates having excellent transparency(transparent substrates) and is more preferably selected from polyesterfilms (in particular, films of PETs and PENs), cycloolefin polymersfilms, polycarbonate films, TAC films, and PMMA films.

The plastic substrate may include one or more additives as needed.Non-limiting examples of the additives include antioxidants, ultravioletabsorbers, photostabilizers, thermal stabilizers, crystal nucleators,flame retardants, flame retardant promotors, fillers, plasticizers,impact modifiers, reinforcers, dispersing agents, antistatic agents,blowing agents, antimicrobial agents, and any other additives. Theplastic substrate may include each of different additives alone or incombination.

The plastic substrate may have a single-layer structure or a multilayerstructure and is not limited in structure (configuration). For example,the plastic substrate for use herein may be selected from plasticsubstrates each having a multilayer structure and including a plasticfilm, and another layer disposed on at least one side of the plasticfilm. The “other layer” refers to a layer other than the hard coat layeraccording to the present invention. Examples of the multilayer structureinclude a structure including the plastic film and the other layerdisposed in this order; and a structure including the other layer, theplastic film, and the other layer disposed in this order. Non-limitingexamples of the other layer include hard coat layers other than the hardcoat layer according to the present invention. Exemplary materialsconstituting the other layer include the plastic materials.

The plastic substrate may have undergone a surface treatment in part orall of its surface. Non-limiting examples of the surface treatmentinclude roughening treatment, adhesion facilitating treatment,antistatic treatment, sand blasting (sand matting), corona dischargetreatment, plasma treatment, chemical etching, water matting, flametreatment, acid treatment, alkaline treatment, oxidation, ultravioletirradiation, silane coupling agent treatment, and any other known orcommon surface treatments. The plastic substrate may be an unorientedfilm or an oriented film (e.g., uniaxially oriented film or biaxiallyoriented film).

The plastic substrate may be produced by a known or common process. Forexample, the plastic substrate may be produced by a process of formingthe plastic material into a film to give the plastic substrate (plasticfilm); or by a process of further forming an appropriate layer (e.g.,the other layer) as needed on the prepared plastic film, and/orsubjecting the plastic film to an appropriate surface treatment. Theplastic substrate may also be selected from commercial products.

The thickness of the substrate is not limited, but may be selected asappropriate within the range of typically from 0.01 to 10000 μm.

The hard coat layer according to the present invention in the hard coatfilm according to the present invention is a layer constituting at leastone surface layer of the hard coat film according to the presentinvention and is a layer (cured product layer) including a cured product(cured resin product) of the curable composition (hard coatlayer-forming curable composition) according to the present invention.

The hard coat layer according to the present invention may have athickness not limited, but of preferably 1 to 200 μm, and morepreferably 3 to 150 μm. When the hard coat film includes the hard coatlayers according to the present invention on both sides of thesubstrate, the “thickness” refers to the thickness of each (single) hardcoat layer. In particular, the hard coat layer according to the presentinvention can maintain high surface hardness (e.g., can maintain apencil hardness of H or higher), even when the hard coat layer has asmall thickness (e.g., a thickness of 5 μm or less). In addition, thehard coat layer is resistant to defects such as cracking due typicallyto cure shrinkage, even when the hard coat layer has a large thickness(e.g., a thickness of 50 μm or more). This allows the hard coat layer tohave a large thickness and to thereby have a significantly higher pencilhardness (e.g., a pencil hardness of 9H or higher).

The hard coat layer according to the present invention may have a hazenot limited, but of preferably 1.5% or less, and more preferably 1.0% orless, at a thickness of 50 μm. The lower limit of the haze is notlimited, but typically 0.1%. The hard coat layer, when having a haze of,in particular, 1.0% or less, tends to be advantageously usable typicallyin uses that require very high transparency. For example, the hard coatlayer is advantageously usable typically as or in surface-protectingsheets in displays such as touch screens. The haze of the hard coatlayer according to the present invention may be measured in conformityto JIS K 7136.

The hard coat layer according to the present invention may have a totalluminous transmittance not limited, but of preferably 85% or more, andmore preferably 90% or more, at a thickness of 50 μm. The upper limit ofthe total luminous transmittance is not limited, but typically 99%. Thehard coat layer, when having a total luminous transmittance of, inparticular, 85% or more, tends to be advantageously usable typically inuses that require very high transparency. For example, the hard coatlayer is advantageously usable typically as or in surface-protectingsheets in displays such as touch screens. The total luminoustransmittance of the hard coat layer according to the present inventionmay be measured in conformity to JIS K 7361-1.

The hard coat film according to the present invention may furtherinclude a surface-protecting film on or over the hard coat layeraccording to the present invention. The hard coat film according to thepresent invention, when including the surface-protecting film, tends tohave still better punching processability. Assume that the hard coatfilm includes the surface-protecting film as mentioned above. In thiscase, the hard coat film can undergo punching using a Thomson bladewithout troubles such as delamination (peeling) from the substrate andcracking, even when, for example, the hard coat layer has very highhardness and is susceptible to these troubles upon punching.

The surface-protecting film may be selected from, but is not limited to,known or common surface-protecting films, such as one including aplastic film and a pressure-sensitive adhesive layer on the plasticfilm. Non-limiting examples of the plastic film include plastic filmsmade from plastic materials including polyesters such as (poly(ethyleneterephthalate)s and poly(ethylene naphthalate)s; polyolefins such aspolyethylenes, polypropylenes, and cycloolefin polymers; polystyrenes;acrylic resins; polycarbonates; epoxy resins; fluorocarbon resins;silicone resins; diacetate resins; triacetate resins; polyarylates;poly(vinyl chloride)s; polysulfones; polyethersulfones; poly(ether etherimide)s; polyimides; and polyamides. Non-limiting examples of thepressure-sensitive adhesive layer include pressure-sensitive adhesivelayers each derived from (or including) one or more of known or commonpressure-sensitive adhesives. Examples of the pressure sensitiveadhesives include, but are not limited to, pressure-sensitive adhesivesbased on any of acrylic polymers, natural rubbers, synthetic rubbers,ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic estercopolymers, styrene-isoprene block copolymers, and styrene-butadieneblock copolymers. The pressure-sensitive adhesive layer may contain oneor more additives such as antistatic agents and slipping agents. Each ofthe plastic film and the pressure-sensitive adhesive layer mayindependently have a single-layer structure or a multilayer structure.The thickness of the surface-protecting film is not limited and may beselected as appropriate.

The surface-protecting film is available from the market as commercialproducts typically under the trade names SUNYTECT Series (from Sun A.Kaken Co., Ltd.), the trade names E-MASK Series (from Nitto DenkoCorporation), the trade names MASTACK Series (from Fujimori Kogyo Co.,Ltd), the trade names HITALEX Series (from Hitachi Chemical Company,Ltd.), and the trade names ALPHAN Series (from Oji F-Tex Co., Ltd.).

The hard coat film according to the present invention may be produced inconformity to any known or common method for producing a hard coat filmwithout limitation. For example, the hard coat film may be produced byapplying the curable composition (hard coat layer-forming curablecomposition) according to the present invention onto at least one sideof the substrate, as needed drying the applied layer to remove thesolvent, and curing the curable composition (curable composition layer).Conditions for curing of the curable composition are not limited and areselectable as appropriate typically from the conditions for theformation of the cured product.

In particular, the hard coat layer according to the present invention inthe hard coat film according to the present invention is a hard coatlayer formed from (derived from) the curable composition (hard coatlayer-forming curable composition) according to the present invention,which is capable of giving a cured product that is highly flexible andhas excellent processability. This allows the hard coat film accordingto the present invention to be producible by a roll-to-roll process. Thehard coat film according to the present invention, when produced by aroll-to-roll process, can be produced with significantly betterproductivity. Assume that the hard coat film according to the presentinvention is produced by a roll-to-roll process. In this case, the hardcoat film may be produced by any known or common production methodaccording to the roll-to-roll process. Non-limiting examples of theproduction method include Steps A, B, and C as essential steps andperform Steps A, B, and C successively. In Step A, a wound, roll-shapedsubstrate is unwound. In Step B, the curable composition (hard coatlayer-forming curable composition) according to the present invention isapplied onto at least one side of the unwound substrate. Next, theapplied layer is dried as needed to remove the solvent, and the curablecomposition (curable composition layer) is cured to form the hard coatlayer according to the present invention on the substrate to give a hardcoat film. In Step C, the prepared hard coat film is rewound into aroll. The method may further include one or more other steps in additionto Steps A, B, and C.

The hard coat film according to the present invention may have athickness not limited and may have a thickness selected as appropriatewithin the range of 1 to 10000 μm.

The hard coat layer according to the present invention in the hard coatfilm according to the present invention may have a surface pencilhardness not limited, but of preferably H or higher, more preferably 2Hor higher, and furthermore preferably 6H or higher. The pencil hardnessmay be determined in conformity to the method prescribed in JIS K5600-5-4.

The hard coat film according to the present invention may have a hazenot limited, but of preferably 1.5% or less, and more preferably 1.0% orless. The lower limit of the haze is not limited, but is typically 0.1%.The hard coat film, when having a haze of, in particular, 1.0% or lesstends to be advantageously usable typically in uses that require veryhigh transparency. For example, the hard coat film is advantageouslyusable typically as or in surface-protecting sheets in displays such astouch screens. The haze of the hard coat film according to the presentinvention is easily controllable within the range typically by using anyof the transparent substrates as the substrate. The haze may be measuredin conformity to JIS K 7136.

The hard coat film according to the present invention may have a totalluminous transmittance not limited, but of preferably 85% or more, andmore preferably 90% or more. The upper limit of the total luminoustransmittance is not limited, but is typically 99%. The hard coat film,when having a total luminous transmittance of, in particular, 90% ormore, tends to be advantageously usable typically in uses that requirevery high transparency. For example, the hard coat film isadvantageously usable typically as or in surface-protecting sheets indisplays such as touch screens. The total luminous transmittance of thehard coat film according to the present invention is easily controllablewithin the range typically by using any of the transparent substrates asthe substrate. The total luminous transmittance may be measured inconformity to JIS K 7361-1.

The hard coat film according to the present invention is still flexible,and is producible and processable by a roll-to-roll process even whilesustaining high hardness and good heat resistance. The hard coat film,as having this configuration, has high quality and offers excellentproductivity. In particular, the hard coat film, when including thesurface-protecting film on or over the hard coat layer according to thepresent invention, further offers excellent punching processability. Thehard coat film is therefore preferably usable in every use that requiresthese properties. For example, the hard coat film according to thepresent invention is usable typically as surface-protecting films invarious products; as surface-protecting films in members or parts ofvarious products; and as components of various products or of members orparts of the products. Non-limiting examples of the products includedisplay devices such as liquid crystal displays and organicelectroluminescent displays; input devices such as touch screens; solarcells; various household electrical appliances; variouselectrical-electronic products; various electrical-electronic productsincluding portable electronic terminals such as game equipment, personalcomputers, tablet computers, smartphones, and cellular phones; andvarious optical devices. In embodiments, the hard coat film according tothe present invention is used as components of various products, or ofmembers or parts of the products. For example, in an embodiment, thehard coat film is used in a touch screen and constitutes a laminateincluding the hard coat film and a transparent conductive film.

The curable composition according to the present invention, when cured,gives a cured product that has surface hardness, heat resistance,flexibility, and processability at excellent levels as described above,and still offers excellent adhesiveness and adhesion to an adherend.Accordingly, the curable composition according to the present inventionis also preferably usable as an adhesive. This adhesive is also referredto as an “adhesive composition”. The adhesive obtained using the curablecomposition according to the present invention as the adhesivecomposition, when cured, is converted into an adhesive member that hassurface hardness, heat resistance, flexibility, processability,adhesiveness, and adhesion at excellent levels. For example, theadhesive is usable as a photocurable adhesive when the curablecomposition according to the present invention contains a cationicphotoinitiator as the curing catalyst; and the adhesive is usable as athermosetting adhesive when the curable composition contains a cationicthermal initiator as the curing catalyst.

The use of the curable composition (adhesive composition) according tothe present invention gives an adhesive sheet (also referred to as“adhesive sheet according to the present invention), which includes asubstrate, and an adhesive layer on or over the substrate. The adhesivelayer is a layer of the curable composition according to the presentinvention. This adhesive layer is also referred to as an “adhesive layeraccording to the present invention”. The adhesive sheet according to thepresent invention may be not only in a sheet form, but also in a formsimilar to a sheet, such as a film form, a tape form, or a plate form.The adhesive sheet according to the present invention may be obtainedtypically, but not limitatively, by applying the curable compositionaccording to the present invention to a substrate and, as needed, dryingthe applied composition. The application (coating) may be performed byany known or common procedure or device without limitation. The dryingmay also be performed with any procedure or device under any conditionswithout limitation. For example, the drying may be performed under suchconditions so as to remove volatile components such as the solvent asmuch as possible and may employ any known or common procedure or device.

The adhesive sheet according to the present invention may be asingle-sided adhesive sheet, which includes an adhesive layer on onlyone side of a substrate; or a double-sided adhesive sheet, whichincludes adhesive layers on both sides of a substrate. When the adhesivesheet according to the present invention is a double-sided adhesivesheet, the adhesive layer according to the present invention has only toconstitute at least one of the adhesive layers. The other adhesive layermay be the adhesive layer according to the present invention or anotheradhesive layer.

The substrate in the adhesive sheet according to the present inventionmay be selected from any of known or common substrates (those for use inadhesive sheets) without limitation. Non-limiting examples of suchsubstrates include plastic substrates, metal substrates, ceramicsubstrates, semiconductor substrates, glass substrates, papersubstrates, woody substrates, and surface-coated substrates. Specificexamples of the substrate are as with the substrate in the hard coatfilm according to the present invention. Typically, the substrate in theadhesive sheet according to the present invention may also be aso-called release liner, or may be one as with the surface-protectingfilm for use in the hard coat film according to the present invention.The adhesive sheet according to the present invention may include thesubstrate as one layer, or as two or more layers. The thickness of thesubstrate is not limited and is selectable as appropriate typicallywithin the range of 1 to 10000 μm.

The adhesive sheet according to the present invention may include eachof different adhesive layers according to the present invention alone orin combination. The thickness of the adhesive layer according to thepresent invention is not limited and is selectable as appropriatetypically within the range of 0.1 to 10000 μm. This is also true for theother adhesive layer. The “other adhesive layer” refers to an adhesivelayer other than the adhesive layer according to the present invention.

The adhesive sheet according to the present invention may furtherinclude one or more other layers in addition to the substrate and theadhesive layer(s). The other layer is exemplified by, but is not limitedto, intermediate layers and under coats.

The use of the curable composition (adhesive composition) according tothe present invention gives a laminate (laminated assembly) (alsoreferred to as “laminate according to the present invention”), whichincludes three or more layers (at least three layers). The at leastthree layers include two adherend layers, and an adhesive layer disposedbetween the two adherend layers. The adhesive layer serves as a layerthat bonds the adherend layers with each other. The adhesive layer is alayer of the cured product of the curable composition according to thepresent invention. This adhesive layer is also referred to as an“adhesive layer according to the present invention”. The laminateaccording to the present invention may be obtained typically, but notlimitatively, by forming an adhesive layer according to the presentinvention on one of the two adherend layers, applying the other adherendlayer to the formed adhesive layer, and then subjecting the resultingarticle typically to light irradiation and/or heating to cure theadhesive layer according to the present invention. The formation of theadhesive layer may be performed typically in a manner as with theadhesive layer in the adhesive sheet according to the present invention.Assume that the laminate according to the present invention is preparedusing a single-sided adhesive sheet as the adhesive sheet according tothe present invention. In this case, the laminate may be obtained byapplying the adhesive sheet according to the present invention to anadherend layer, and subjecting the resulting article typically to lightirradiation and/or heating to cure the adhesive layer according to thepresent invention in the adhesive sheet. In the resulting laminate, thesubstrate in the adhesive sheet according to the present inventioncorresponds to an adherend layer. Assume that the laminate according tothe present invention is prepared typically using the adhesive sheetaccording to the present invention that is a double-sided adhesive sheetincluding a release liner as the substrate (carrier). In this case, thelaminate may be obtained by applying the adhesive sheet according to thepresent invention to one adherend layer, removing the release liner toexpose the adhesive layer, applying the other adherend layer to theexposed adhesive layer, and subjecting the resulting article typicallyto light irradiation and/or heating to cure the adhesive layer accordingto the present invention. However, the method for producing the laminateaccording to the present invention is not limited to the methodsmentioned above.

The adherend in the laminate according to the present invention is notlimited and is exemplified as with the substrate in the hard coat filmaccording to the present invention. The laminate according to thepresent invention may include only two adherend layers or include threeor more adherend layers. The thickness of the adherend layer is notlimited and may be selected as appropriate typically within the range of1 to 100000 μm. The adherend does not have to have a layer form in astrict sense.

The laminate according to the present invention may include each ofdifferent adhesive layers according to the present invention alone or incombination. The thickness of the adhesive layer according to thepresent invention is not limited and may be selected as appropriatetypically within the range of 0.1 to 10000 μm.

The laminate according to the present invention may include one or moreother layers in addition to the adherend(s) and the adhesive layer(s) inthe present invention. The other layers are exemplified by, but are notlimited to, intermediate layers, under coats, and other adhesive layers.

The curable composition (adhesive composition) according to the presentinvention is usable not only for the preparation of the adhesive sheetaccording to the present invention and the laminate according to thepresent invention, but for other various uses in which desired articles(e.g., parts) are bonded with each other.

EXAMPLES

The present invention will be illustrated in further detail withreference to several examples below. It should be noted, however, thatthe examples are by no means intended to limit the scope of the presentinvention. The molecular weight of each product was measured usingAlliance HPLC System 2695 (supplied by Waters Corporation), RefractiveIndex Detector 2414 (supplied by Waters Corporation), two TskgelGMH_(HR)-M columns (supplied by Tosoh Corporation) with a Tskgel guardcolumn H_(HR)L (supplied by Tosoh Corporation) as a guard column, COLUMNHEATER U-620 (supplied by Sugai) as a column oven, and THF solvent, at ameasurement temperature of 40° C. The T3 to T2 ratio of the T2 unit tothe T3 unit in the product was measured by ²⁹Si-NMR spectrometry withJEOL ECA500 (500 MHz). The 5% weight loss temperature T_(d5) of theproduct was measured by thermogravimetry (TGA) in an air atmosphere at arate of temperature rise of 5° C./min.

Hereinafter the blending amounts of the trade names HS-1PC, CPI-101A,UV9380C, HS-1A, and SI-100L are each indicated in terms of solidscontent.

Example 1

Materials used were 161.5 mmol (39.79 g) of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter also referredto as “EMS”), 9 mmol (1.69 g) of phenyltrimethoxysilane (hereinafteralso referred to as “PMS”), and 165.9 g of acetone. In a nitrogenstream, the materials were placed in a 300-ml flask (reactor) equippedwith a thermometer, a stirrer, a reflux condenser, and a nitrogen inlettube, followed by temperature rise to 50° C. to give a mixture. To theprepared mixture, was added dropwise 4.70 g (1.7 mmol in terms ofpotassium carbonate) of a 5% aqueous solution of potassium carbonateover 5 minutes, followed by 1700 mmol (30.60 g) of water added dropwiseover 20 minutes. No significant temperature rise occurred during thedropwise additions. The mixture was then subjected to a polycondensationreaction in a nitrogen stream for 4 hours while keeping the temperatureat 50° C.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1911and a molecular-weight dispersity of 1.47. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 10.3, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled, washed with water until alower layer liquid became neutral, and an upper layer liquid wasisolated. The solvent was distilled off from the upper layer liquid at40° C. and 1 mmHg. This yielded a colorless, transparent, liquid product(an epoxy-containing polyorganosilsesquioxane). The product had a T_(d5)of 370° C.

Examples 2 to 6 and Comparative Examples 1 and 2

Epoxy-containing polyorganosilsesquioxanes were produced each by aprocedure similar to that in Example 1, except for changing the amountsof the starting materials (EMS and PMS), the type and amount of thesolvent, the reaction temperature, the amount of the 5% potassiumcarbonate aqueous solution, the amount of water, and the reaction timeas given in Table 1. Table 1 presents the number-average molecularweight (Mn), the molecular-weight dispersity, the T3 to T2 ratio of theT3 unit to the T2 unit, and the T_(d5) of the epoxy-containingpolyorganosilsesquioxanes prepared in the examples and comparativeexamples. The T_(d5) in Table 1 is indicated in degree Celsius (° C.).

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Com.Ex. 1 Com. Ex. 2 Silsesquioxane EMS (g) 39.79 39.79 39.79 39.79 39.7949.28 19.71 19.71 production PMS (g) 1.69 1.69 1.69 1.69 1.69 0 23.823.8 Solvent acetone dioxane acetone acetone acetone acetone dioxaneacetone Solvent amount (g) 165.9 165.9 165.9 83.0 165.9 165.9 174.03174.3 Reaction temperature (° C.) 50 70 50 50 50 50 30 50 5% K₂CO₃ aq(g) 4.70 4.70 4.70 4.70 4.70 4.70 4.70 5.53 H₂O (g) 30.6 15.3 30.6 30.630.6 30.6 15.3 36 Reaction time (hr) 4 2 1 3 7 5 2 5 SilsesquioxaneSample name S-1 S-2 S-3 S-4 S-5 S-7 S-6 S-8 Mn 1911 1248 1429 2496 20501808 971 1795 Molecular-weight dispersity 1.47 1.18 1.37 1.78 1.64 1.471.16 1.7 T3 to T2 ratio 10.3 5.7 6.0 12.2 11.2 11.0 0.6 15.1 T_(d5) 370371 385 360 363 374 260 394

The polyorganosilsesquioxanes prepared in Examples 1 to 6 were subjectedto FT-IR spectra measurement with the apparatus under conditionsmentioned above and were each found to have one intrinsic absorptionpeak at about 1100 cm⁻¹.

Example 7

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of a curing catalyst 1([diphenyl[4-(phenylthio)phenyl]sulfoniumtris(pentafluoroethyl)trifluorophosphate]).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 5 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking) and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of312 mJ/cm² and an irradiation intensity of 80 W/cm². Lastly, the articlewas subjected to a heat treatment (aging) at 80° C. for 2 hours to curethe layer of the applied hard-coating composition. This yielded a hardcoat film including the hard coat layer.

Examples 8 to 17 and 19, and Comparative Examples 3 and 4

Hard-coating compositions were prepared each by a procedure similar tothat in Example 7, except for changing the formulation of thehard-coating composition (curable composition) and the thickness of thehard coat layer, as given in Table 2. Hard coat films were prepared eachby a procedure similar to that in Example 7, except for using theprepared corresponding hard-coating composition and changing thethickness of the hard coat layer as given in Table 2. In Table 2, theblending amounts of starting materials for the curable compositions areindicated in part by weight.

Example 18

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name SI-100L (a thermal acid generator,supplied by SANSHIN CHEMICAL INDUSTRY CO., LTD.).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 25 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes and then subjected to a heat treatmentat 150° C. for one hour to thermally cure the layer of the appliedhard-coating composition. This gave a hard coat film including the hardcoat layer.

The above-prepared hard coat film was examined and evaluated on variouspoints according to methods as follows. Results are presented in Table2.

(1) Haze and Total Luminous Transmittance

The haze and the total luminous transmittance of the above-prepared hardcoat film were measured using a haze meter (NDH-300A, supplied by NipponDenshoku Industries Co., Ltd.).

(2) Surface Hardness (Pencil Hardness)

The pencil hardness of the hard coat layer surface of the above-preparedhard coat film was evaluated in conformity to JIS K 5600-5-4.

(3) Heat Resistance (5% Weight Loss Temperature (T_(d5)))

A hard coat film was prepared by the procedure as above, except forusing a glass plate instead of the PET film. About 5 mg of the hard coatlayer in the hard coat film was cut out using a cutter, and this wasused as a sample. The 5% weight loss temperature of the sample wasmeasured using a thermogravimeter/differential thermal analyzer (TG/DTA6300, supplied by Seiko Instruments Inc.) under conditions as follows:

Measurement temperature range: 25° C. to 550° C.

Rate of temperature rise: 10° C./min.

Gas atmosphere: nitrogen

(4) Scratch Resistance

The hard coat layer surface in the above-prepared hard coat film wasrubbed by 100 reciprocating movements of a steel wool #0000 under a loadof 1000 g/cm². Whether and how many scratches were formed on the hardcoat layer surface were examined, and the scratch resistance wasevaluated according to criteria as follows:

Very good (VG) (very good scratch resistance): no scratch was formed;

Good (good scratch resistance): one to ten scratches were formed; and

Poor (poor scratch resistance): greater than ten scratches were formed.

(5) Flexibility (Cylindrical Mandrel Method): Mandrel Test

The flexibility of the above-prepared hard coat film was evaluated usinga cylindrical mandrel in conformity to JIS K 5600-5-1.

TABLE 2 Example Example Example Example Example Example Example Example7 8 9 10 11 12 13 14 Curable Silsesquioxane S-2 — — — 100 100 — — —composition S-1 100 100 100 — — — — 100 S-3 — — — — — 100 — — S-4 — — —— — — 100 — S-6 — — — — — — — — S-7 — — — — — — — — S-8 — — — — — — — —Initiator CPI-210S 1 1 1 1 1 1 1 — HS-1PC — — — — — — — 1 CPI-101A — — —— — — — — UV9380C — — — — — — — — HS-1A — — — — — — — — SI-100L — — — —— — — — Solvent Methyl 20 20 20 20 20 20 20 20 isobutyl ketoneEvaluations Hard coat layer thickness 5 25 50 5 115 25 20 30 (μm) Haze(%) 0.92 0.91 1.0 0.96 0.93 0.97 0.67 0.66 Total luminous 91 91 91 91 9191 92 91 transmittance (%) Pencil hardness 4H 6H 9H 2H 9H 3H 4H 9HT_(d5) (° C.) 330 340 333 328 342 331 329 383 Scratch resistance Good VGVG Good VG Good Good VG (1 kg/cm²) Mandrel test (diameter) 2 12 32 2 >3216 12 20 Example Example Example Example Example Com. Com. 15 16 17 1819 Ex. 3 Ex. 4 Curable Silsesquioxane S-2 — — — — — — — composition S-1100 100 100 100 — — — S-3 — — — — — — — S-4 — — — — — — — S-6 — — — — —100 — S-7 — — — — 100 — — S-8 — — — — — — 100 Initiator CPI-210S — — — —— 1 — HS-1PC — — — — 1 — 1 CPI-101A 1 — — — — — — UV9380C — 1 — — — — —HS-1A — — 1 — — — — SI-100L — — — 1 — — — Solvent Methyl 20 20 20 20 2020 20 isobutyl ketone Evaluations Hard coat layer thickness 35 40 40 2530 5 30 (μm) Haze (%) 1.31 0.61 0.42 1.0 1.5 0.98 1.7 Total luminous 9191 91 91 91 91 90 transmittance (%) Pencil hardness 8H 9H 7H 7H 9H 68 HT_(d5) (° C.) 437 384 410 436 373 321 390 Scratch resistance VG VG VG VGVG Poor Good (1 kg/cm²) Mandrel test (diameter) 25 32 32 16 20 2 2

The abbreviations given in Table 2 refer to as follows. The sample namesof polyorganosilsesquioxanes correspond to the sample names given inTable 1.

Curing catalyst 1: [diphenyl[4-(phenylthio)phenyl]sulfoniumtris(pentafluoroethyl)trifluorophosphate], a photoacid generator

HS-1PC: trade name HS-1PC (supplied by San-Apro Ltd.), a photoacidgenerator

CPI-101A: trade name CPI-101A (supplied by San-Apro Ltd.), a photoacidgenerator

UV9380C: trade name UV9380C (supplied by Momentive Performance MaterialsJapan LLC), a photoacid generator

HS-1A: trade name HS-1A (supplied by San-Apro Ltd.), a photoacidgenerator

SI-100L: trade name San-Aid SI-100L (supplied by SANSHIN CHEMICALINDUSTRY CO., LTD.), a thermal acid generator

Example 20

A surface-protecting film (MASTACK NBO-0424, supplied by Fujimori KogyoCo., Ltd.) was applied onto the hard coat layer of the hard coat filmprepared in Example 14 and yielded a hard coat film bearing thesurface-protecting film. The resulting hard coat film was subjected topunching using a dumbbell sample cutting machine equipped with the SuperDumbbell Cutter (Model: SDK-500-D, in conformity to JIS K 7133-2). Itwas demonstrated that the hard coat film could be punched withoutdelamination (peeling) of the hard coat layer from the substrate andwithout cracking of the hard coat layer.

FIG. 1 illustrates a photomicrograph (100-fold magnification) of ends ofthe hard coat film after the punching, where the photomicrograph wastaken with a digital microscope. As illustrated in FIG. 1 , neitherdelamination of the hard coat layer from the substrate nor cracking inthe hard coat layer occurred.

Example 21

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name HS-1PC (a photoacid generator, suppliedby San-Apro Ltd.).

The above-prepared hard-coating composition was applied onto a 78-μmthick TAC film (#80, supplied by Daicel Corporation) by flow castingusing a wire bar so as to form a hard coat layer having a thicknessafter curing of 50 μm. The resulting article was left stand in an ovenat 70° C. for 10 minutes (for prebaking) and then irradiated with anultraviolet ray under irradiation conditions at an irradiance of 312mJ/cm² and an irradiation intensity of 80 W/cm²). Lastly, the articlewas subjected to a heat treatment (aging) at 80° C. for 2 hours to curethe layer of the applied hard-coating composition. This yielded a hardcoat film including the hard coat layer.

Example 22

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name HS-1PC (a photoacid generator, suppliedby San-Apro Ltd.).

The above-prepared hard-coating composition was applied onto a 300-μmthick cycloolefin copolymer film (trade name TOPAS 6013, supplied byPolyplastics Co., Ltd.) by flow casting using a wire bar so as to form ahard coat layer having a thickness after curing of 45 μm. The resultingarticle was left stand in an oven at 70° C. for 10 minutes (forprebaking) and then irradiated with an ultraviolet ray under irradiationconditions at an irradiance of 312 mJ/cm² and an irradiation intensityof 80 W/cm². Lastly, the article was subjected to a heat treatment(aging) at 80° C. for 2 hours to cure the layer of the appliedhard-coating composition. This yielded a hard coat film including thehard coat layer.

Example 23

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name HS-1PC (a photoacid generator, suppliedby San-Apro Ltd.).

The above-prepared hard-coating composition was applied onto a 2024-μmthick acrylic polymer film (trade name SUMIPEX X, supplied by SumitomoChemical Co., Ltd.) by flow casting using a wire bar so as to form ahard coat layer having a thickness after curing of 32 μm. The resultingarticle was left stand in an oven at 70° C. for 10 minutes (forprebaking) and then irradiated with an ultraviolet ray under irradiationconditions at an irradiance of 312 mJ/cm² and an irradiation intensityof 80 W/cm². Lastly, the article was subjected to a heat treatment(aging) at 80° C. for 2 hours to cure the layer of the appliedhard-coating composition. This yielded a hard coat film including thehard coat layer.

Example 24

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name HS-1PC (a photoacid generator, suppliedby San-Apro Ltd.).

The above-prepared hard-coating composition was applied onto a 129-μmthick PEN film (trade name Teonex #125, supplied by Teijin DuPont FilmsJapan Limited) by flow casting using a wire bar so as to form a hardcoat layer having a thickness after curing of 34 μm. The resultingarticle was left stand in an oven at 70° C. for 10 minutes (forprebaking) and then irradiated with an ultraviolet ray under irradiationconditions at an irradiance of 312 mJ/cm² and an irradiation intensityof 80 W/cm². Lastly, the article was subjected to a heat treatment(aging) at 80° C. for 2 hours to cure the layer of the appliedhard-coating composition. This yielded a hard coat film including thehard coat layer.

Example 25

A solution mixture was prepared as a hard-coating composition (curablecomposition) by blending 100 parts by weight of the epoxy-containingpolyorganosilsesquioxane (S-1) prepared in Example 1, 20 parts by weightof methyl isobutyl ketone (supplied by Kanto Chemical Co., Inc.), and 1part by weight of the trade name HS-1PC (a photoacid generator, suppliedby San-Apro Ltd.).

The above-prepared hard-coating composition was applied onto a 100-μmthick polycarbonate film (trade name SUNLOID PC, supplied by SumitomoBakelite Co., Ltd.) by flow casting using a wire bar so as to form ahard coat layer having a thickness after curing of 45 μm. The resultingarticle was left stand in an oven at 70° C. for 10 minutes (forprebaking) and then irradiated with an ultraviolet ray under irradiationconditions at an irradiance of 312 mJ/cm² and an irradiation intensityof 80 W/cm². Lastly, the article was subjected to a heat treatment(aging) at 80° C. for 2 hours to cure the layer of the appliedhard-coating composition. This yielded a hard coat film including thehard coat layer.

The hard coat films prepared in Examples 21 to 25 were examined tomeasure and evaluate the haze and total luminous transmittance of thehard coat film, and the pencil hardness of the hard coat layer surface.The haze, total luminous transmittance, and pencil hardness weremeasured and evaluated by the above-mentioned methods.

Table 3 also presents the measurement and evaluation results of thehaze, total luminous transmittance, and pencil hardness (substratesurface) of the substrate (substrate alone) in the hard coat filmsprepared in Examples 21 to 25.

TABLE 3 Hard coat Total Substrate Total layer luminous thicknessthickness thickness Haze transmittance Pencil (□m) (□m) (□m) (%) (%)hardness Example 21 Hard coat film 78 128 50 0.78 41.22 9H Substratealone (TAC #80) 78 78 — 0.44 41.59 H Example 22 Hard coat film 300 34545 0.47 91.81 2H Substrate alone (TOPAS 6013) 300 300 — 0.43 92.11 6B orlower Example 23 Hard coat film 2024 2056 32 1.02 79.1 6H Substratealone (SUMIPEX X) 2024 2024 — 0.14 80.19 4B Example 24 Hard coat film129 163 34 3.09 39.82 7H Substrate alone (Teonex #125) 129 129 — 0.8939.39 H Example 25 Hard coat film 100 145 45 0.58 91.27 HB Substratealone (SUNLOID PC) 100 100 — 0.12 91.85 6B or lower

As indicated in Tables 2 and 3, the hard coat films according to thepresent invention had very high surface hardness as compared with thecorresponding substrates devoid of the hard coat layer according to thepresent invention. The hard coat films also maintained equivalentoptical properties (transparency) as compared with the substrates. Inaddition, it was demonstrated that the hard coat films according to thepresent invention are applicable to a variety of substrates assubstrates constituting the hard coat films.

Example 26

Materials used were 1757.5 mmol (433.0 g) of2-(3,4-epoxy)cyclohexylethyltrimethoxysilane (EMS), 93 mmol (18.34 g) ofphenyltrimethoxysilane (PMS), and 1805.4 g of acetone. In a nitrogenstream, the materials were placed in a 5-liter separable flask (reactor)equipped with a thermometer, a stirrer, a reflux condenser, and anitrogen inlet tube, followed by temperature rise to 50° C. to give amixture. To the prepared mixture, was added dropwise 51.14 g (18.5 mmolin terms of potassium carbonate) of a 5% aqueous solution of potassiumcarbonate over 5 minutes, followed by 18.5 mol (333.0 g) of water over20 minutes. No significant temperature rise occurred during the dropwiseadditions. While keeping the temperature at 50° C., the mixture was thensubjected to a polycondensation reaction in a nitrogen stream for 5hours.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1800and a molecular-weight dispersity of 1.55. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 10.3, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled and, simultaneously,combined with 902.7 g of methyl isobutyl ketone and 660 g of a 5% sodiumchloride aqueous solution, followed by water washing. After separation,the aqueous layer was drawn out, the residual liquid was combined againwith 902.7 g of methyl isobutyl ketone and washed with water until alower layer liquid became neutral. The upper layer liquid was isolated,from which the solvent was distilled off at 50° C. and 1 mmHg. Thisyielded about 457 g of a colorless, transparent, liquid product(epoxy-containing polyorganosilsesquioxane; polyorganosilsesquioxanehaving an epoxy content of 95% by mole and a phenyl content of a 5% bymole). The product contained 27.23% by weight of methyl isobutyl ketone.

Example 27

Materials used were 200.0 mmol (49.29 g) of2-(3,4-epoxy)cyclohexylethyltrimethoxysilane (EMS) and 197.1 g ofacetone. In a nitrogen stream, the materials were placed in a 5-literseparable flask (reactor) equipped with a thermometer, a stirrer, areflux condenser, and a nitrogen inlet tube, followed by temperaturerise to 50° C. to give a mixture. To the prepared mixture, was addeddropwise 5.53 g (2.0 mmol in terms of potassium carbonate) of a 5%aqueous solution of potassium carbonate over 5 minutes, followed by 2.0mol (36.0 g) of water over 20 minutes. No significant temperature riseoccurred during the dropwise additions. While keeping the temperature at50° C., the mixture was then subjected to a polycondensation reaction ina nitrogen stream for 5 hours.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1720and a molecular-weight dispersity of 1.55. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 11.0, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled and, simultaneously,combined with 98.4 g of methyl isobutyl ketone and 68.2 g of a 5% sodiumchloride aqueous solution, followed by water washing. After separation,the aqueous layer was drawn out, and the residual liquid was combinedagain with 98.4 g of methyl isobutyl ketone and was washed with wateruntil a lower layer liquid became neutral. An upper layer liquid wasisolated, from which the solvent was distilled off at 50° C. and 1 mmHg.This yielded about 53 g of a colorless, transparent, liquid product(epoxy-containing polyorganosilsesquioxane; polyorganosilsesquioxanehaving an epoxy content of 100% by mole). The product contained 33.78%by weight of methyl isobutyl ketone.

The silsesquioxane prepared in Example 26 had a T3 to T2 ratio of 10.3,and the silsesquioxane prepared in Example 27 had a T3 to T2 ratio of11.0. Both the silsesquioxanes were found to partially include the T2unit.

Example 28

Materials used were 237.5 mmol (58.52 g) of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EMS), 13 mmol (2.95 g) of3-glycidyloxypropyltrimethoxysilane (hereinafter also referred to as“GMS”), and 245.9 g of acetone. In a nitrogen stream, the materials wereplaced in a 500-ml flask (reactor) equipped with a thermometer, astirrer, a reflux condenser, and a nitrogen inlet tube, followed bytemperature rise to 50° C. to give a mixture. To the prepared mixture,was added dropwise 6.91 g (2.5 mmol in terms of potassium carbonate) ofa 5% aqueous solution of potassium carbonate over 5 minutes, followed by2500 mmol (45.00 g) of water over 20 minutes. No significant temperaturerise occurred during the dropwise additions. While keeping thetemperature at 50° C., the mixture was then subjected to apolycondensation reaction in a nitrogen stream for 5 hours.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1782and a molecular-weight dispersity of 1.52. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 9.5:1, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled and washed with wateruntil a lower layer liquid became neutral. An upper layer liquid wasisolated, from which the solvent was distilled off at 50° C. and 1 mmHg.This yielded 60 g of a colorless, transparent, liquid product(epoxy-containing polyorganosilsesquioxane) containing 17.81% by weightof MIBK.

Example 29

Materials used were 200.0 mmol (49.28 g) of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EMS), 50 mmol (11.82 g) of3-glycidyloxypropyltrimethoxysilane (GMS), and 244.4 g of acetone. In anitrogen stream, the materials were placed in a 500-ml flask (reactor)equipped with a thermometer, a stirrer, a reflux condenser, and anitrogen inlet tube, followed by temperature rise to 50° C. to give amixture. To the prepared mixture, was added dropwise 6.91 g (2.5 mmol interms of potassium carbonate) of a 5% aqueous solution of potassiumcarbonate over 5 minutes, followed by 2500 mmol (45.00 g) of water over20 minutes. No significant temperature rise occurred during the dropwiseadditions. While keeping the temperature at 50° C., the mixture was thensubjected to a polycondensation reaction in a nitrogen stream for 5hours.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1725and a molecular-weight dispersity of 1.47. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 10.5:1, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled and washed with wateruntil a lower layer liquid became neutral. An upper layer liquid wasisolated, from which the solvent was distilled off at 50° C. and 1 mmHg.This yielded 60 g of a colorless, transparent, liquid product(epoxy-containing polyorganosilsesquioxane) containing 25.84% by weightof MIBK.

Example 30

Materials used were 150.0 mmol (36.96 g) of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EMS), 350 mmol (82.72 g)of 3-glycidyloxypropyltrimethoxysilane (GMS), and 478.7 g of acetone. Ina nitrogen stream, the materials were placed in a 1000-ml flask(reactor) equipped with a thermometer, a stirrer, a reflux condenser,and a nitrogen inlet tube, followed by temperature rise to 50° C. togive a mixture. To the prepared mixture, was added dropwise 13.82 g (5mmol in terms of potassium carbonate) of a 5% aqueous solution ofpotassium carbonate over 5 minutes, followed by 5000 mmol (90.00 g) ofwater over 20 minutes. No significant temperature rise occurred duringthe dropwise additions. While keeping the temperature at 50° C., themixture was then subjected to a polycondensation reaction in a nitrogenstream for 5 hours.

A product in the reaction mixture after the polycondensation reactionwas analyzed and found to have a number-average molecular weight of 1500and a molecular-weight dispersity of 1.36. The product was found to havea T3 to T2 ratio of the T3 unit to the T2 unit of 8:1, as calculatedfrom the ²⁹Si-NMR spectrum of the product.

Subsequently, the reaction mixture was cooled and washed with wateruntil a lower layer liquid became neutral. An upper layer liquid wasisolated, from which the solvent was distilled off at 50° C. and 1 mmHg.This yielded 114 g of a colorless, transparent, liquid product(epoxy-containing polyorganosilsesquioxane) containing 26.36% by weightof MIBK.

Example 31

Materials used were 1 g (1 g as the product containing 27.23% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 26, 14.6 mg (14.6 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.5 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), and 0.253 g of methyl isobutylketone. The materials were placed in a 6-cc dark brown sample vial,stirred and mixed using a vibrator, and yielded a curable composition(hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking) and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of430 mJ/cm² and an irradiation intensity of 160 W/cm². Lastly, thearticle was subjected to a heat treatment (aging) at 80° C. for 2 hoursto cure the layer of the applied hard-coating composition. This yieldeda hard coat film including the hard coat layer.

The blending amounts of starting materials for the curable compositionsgiven in Tables 4 and 5 are indicated in part by weight. In Tables 4 and5, the blending amounts of the “silsesquioxane prepared in Example 26”,“silsesquioxane prepared in Example 27”, “silsesquioxane prepared inExample 28”, “silsesquioxane prepared in Example 29”, and“silsesquioxane prepared in Example 30” are indicated as amountsexcluding MIBK; and the blending amount of WPI-124 is indicated as anamount excluding the solvent. The contents of the solvents are not shownin Tables 4 and 5.

Example 32

The curable composition (hard-coating composition) prepared in Example31 was applied onto a PET film (trade name KEB03 W, supplied by TeijinDuPont Films Japan Limited) by flow casting using a wire bar so as toform a hard coat layer having a thickness after curing of 30 μm. Theresulting article was left stand in an oven at 70° C. for 10 minutes(for prebaking), and then irradiated with an ultraviolet ray underirradiation conditions at an irradiance of 430 mJ/cm² and an irradiationintensity of 160 W/cm² to cure the layer of the applied hard-coatingcomposition, without heat treatment subsequent to the UV irradiation.This yielded a hard coat film including the hard coat layer.

Example 33

Materials used were 1 g (1 g as the product containing 27.23% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 26, 14.6 mg (14.6 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.5 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.253 g of methyl isobutyl ketone,and 36.4 mg of ethylene glycol monovinyl ether (supplied by TokyoChemical Industry Co., Ltd.). The materials were placed in a 6-cc darkbrown sample vial, stirred and mixed using a vibrator, and yielded acurable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 34

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of ethylene glycol monovinyl ether (supplied by TokyoChemical Industry Co., Ltd.). The materials were placed in a 6-cc darkbrown sample vial, stirred and mixed using a vibrator, and yielded acurable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 35

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of cyclohexanedimethanol monovinyl ether. The materials wereplaced in a 6-cc dark brown sample vial, stirred and mixed using avibrator, and yielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 36

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of triethylene glycol monovinyl ether. The materials wereplaced in a 6-cc dark brown sample vial, stirred and mixed using avibrator, and yielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 37

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of diethylene glycol monovinyl ether. The materials wereplaced in a 6-cc dark brown sample vial, stirred and mixed using avibrator, and yielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 38

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of hydroxybutyl vinyl ether. The materials were placed in a6-cc dark brown sample vial, stirred and mixed using a vibrator, andyielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 39

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of isobutyl vinyl ether. The materials were placed in a 6-ccdark brown sample vial, stirred and mixed using a vibrator, and yieldeda curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 40

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 27, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of cyclohexanedimethanol divinyl ether. The materials wereplaced in a 6-cc dark brown sample vial, stirred and mixed using avibrator, and yielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 41

Materials used were 1 g (1 g as the product containing 33.78% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 26, 13.2 mg (13.2 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), 1.3 mg of the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), 0.104 g of methyl isobutyl ketone,and 33.1 mg of diethylene glycol divinyl ether. The materials wereplaced in a 6-cc dark brown sample vial, stirred and mixed using avibrator, and yielded a curable composition (hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 30 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking), and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of155 mJ/cm² and an irradiation intensity of 160 W/cm² to cure the layerof the applied hard-coating composition, without heat treatmentsubsequent to the UV irradiation. This yielded a hard coat filmincluding the hard coat layer.

Example 42

The hard-coating composition prepared in Example 31 was applied onto aPET film (trade name KEB03 W, supplied by Teijin DuPont Films JapanLimited) by flow casting using a wire bar so as to form a hard coatlayer having a thickness after curing of 30 μm. The resulting articlewas left stand in an oven at 70° C. for 10 minutes (for prebaking), andthen irradiated with an ultraviolet ray under irradiation conditions atan irradiance of 155 mJ/cm² and an irradiation intensity of 160 W/cm² tocure the layer of the applied hard-coating composition, without heattreatment subsequent to the UV irradiation. This yielded a hard coatfilm including the hard coat layer.

Example 43

A hard coat film was prepared by the same procedure under the sameconditions as in Example 34, except for using no vinyl ether compound asa component of the hard-coating composition.

Example 44

Materials used were 1 g (1 g as the product containing 17.81% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 28, 16.4 mg (16.4 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), and 0.37 g of methyl isobutylketone. The materials were placed in a 6-cc dark brown sample vial,stirred and mixed using a vibrator, and yielded a curable composition(hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 40 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking) and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of430 mJ/cm² and an irradiation intensity of 160 W/cm². The article wasleft stand in an oven at 80° C. for 2 hours (for prebaking) to cure thelayer of the applied hard-coating composition. This yielded a hard coatfilm including the hard coat layer.

Example 45

Materials used were 1 g (1 g as the product containing 25.84% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 29, 14.8 mg (14.8 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), and 0.24 g of methyl isobutylketone. The materials were placed in a 6-cc dark brown sample vial,stirred and mixed using a vibrator, and yielded a curable composition(hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 40 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking) and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of430 mJ/cm² and an irradiation intensity of 160 W/cm². The article wasleft stand in an oven at 80° C. for 2 hours (for post-baking) to curethe layer of the applied hard-coating composition. This yielded a hardcoat film including the hard coat layer.

Example 46

Materials used were 1 g (1 g as the product containing 26.36% by weightof MIBK) of the epoxy-containing polyorganosilsesquioxane prepared inExample 30, 14.7 mg (14.7 mg as a 50% solution) of the trade nameWPI-124 (supplied by Wako Pure Chemical Industries, Ltd., a 50% solutionof a photoacid generator), the trade name BYK-307 (supplied byBYK-Chemie GmbH, a leveling agent), and 0.23 g of methyl isobutylketone. The materials were placed in a 6-cc dark brown sample vial,stirred and mixed using a vibrator, and yielded a curable composition(hard-coating composition).

The above-prepared hard-coating composition was applied onto a PET film(trade name KEB03 W, supplied by Teijin DuPont Films Japan Limited) byflow casting using a wire bar so as to form a hard coat layer having athickness after curing of 40 μm. The resulting article was left stand inan oven at 70° C. for 10 minutes (for prebaking) and then irradiatedwith an ultraviolet ray under irradiation conditions at an irradiance of430 mJ/cm² and an irradiation intensity of 160 W/cm². The article wasleft stand in an oven at 80° C. for 2 hours (for post-baking) to curethe layer of the applied hard-coating composition. This yielded a hardcoat film including the hard coat layer.

The hard coat films prepared in Examples 31 to 46 were subjected tovarious evaluations by methods as follows. Results are presented inTables 4 and 5.

(1) Haze and Total Luminous Transmittance The haze and total luminoustransmittance of each of the hard coat films were measured using a hazemeter (NDH-300A, supplied by Nippon Denshoku Industries Co., Ltd.).

(2) Yellowness b*

The yellowness b* of each hard coat film was measured using a differencecolorimeter (NDH-300A, supplied by Nippon Denshoku Industries Co.,Ltd.).

(3) Surface Hardness (Pencil Hardness)

The pencil hardness of the hard coat layer surface in each hard coatfilm was measured in conformity to JIS K 5600-5-4.

(4) Thermal Yellowing after Curing

Each of the hard coat films prepared in Examples 34 to 41 was subjectedto a heat treatment at the heating temperature for the heating time asgiven in “thermal yellowing after curing” in Table 4. The yellowness b*of the hard coat film after the heat treatment was measured using adifference colorimeter (NDH-300A supplied by Nippon Denshoku IndustriesCo., Ltd.). Results are presented in Table 4.

TABLE 4 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam-Exam- ple ple ple ple ple ple ple ple ple ple ple 31 32 33 34 35 36 3738 39 40 41 Curable Epoxy- Silsesquioxane 100 100 100 — — — — — — — 100compo- containing prepared in sition polyorgano- Example 26silsesquioxane Silsesquioxane — — — 100 100 100 100 100 100 100 —prepared in Example 27 Silsesquioxane — — — — — — — — — — — prepared inExample 28 Silsesquioxane — — — — — — — — — — — prepared in Example 29Silsesquioxane — — — — — — — — — — — prepared in Example 30 Vinyl etherEGVE — — 5 5 — — — — — — — compound CHXDM-VE — — — — 5 — — — — — —TEG-VE — — — — — 5 — — — — — DEG-VE — — — — — — 5 — — — — HBVE — — — — —— — 5 — — — IBVE — — — — — — — — 5 — — CHXDMDVE — — — — — — — — — 5 —DEGDVE — — — — — — — — — — 5 Leveling agent BYK-307 0.2 0.2 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 Initiator WPI-124 1 1 1 1 1 1 1 1 1 1 1 CuringUV curing mJ/cm² 430 430 155 155 155 155 155 155 155 155 155 conditions(UV irradiance) Thermal curing ° C. 80 none none none none none nonenone none none none hr 2 none none none none none none none none nonenone Evalu- Hard coat layer thickness (□m) 30 27 30 32 32 36 36 32 35 3235 ations Haze (%) 0.77 0.64 0.58 0.52 0.55 0.9 1.05 1.01 0.5 0.56 0.95Total luminous transmittance (%) 91.85 91.81 91.89 92.03 91.85 91.5591.88 91.9 92.1 91.68 91.82 Yellowness b* 0.79 0.72 0.75 0.64 0.66 0.80.85 0.77 0.72 0.73 0.86 Pencil hardness 9H 9H 8H 9H 9H 9H 8H 8H 9H 9H8H Thermal Heating — — — 80 50 80 80 80 80 80 80 yellowing temperatureafter (° C.) curing Heating time — — — 240 240 240 240 240 240 30 240(min.) Yellowness b* — — — 0.8 0.8 0.94 0.92 1.57 1.49 1.51 1.53 afterheating

TABLE 5 Example Example Example Example Example 42 43 44 45 46 CurableEpoxy-containing Silsesquioxane prepared 100 — — — — compositionpolyorganosilsesquioxane in Example 26 Silsesquioxane prepared — 100 — —— in Example 27 Silsesquioxane prepared — — 100 — — in Example 28Silsesquioxane prepared — — — 100 — in Example 29 Silsesquioxaneprepared — — — — 100 in Example 30 Vinyl ether compound EGVE — — — — —CHXDM-VE — — — — — TEG-VE — — — — — DEG-VE — — — — — HBVE — — — — — IBVE— — — — — CHXDMDVE — — — — — DEGDVE — — — — — Leveling agent BYK-307 0.20.2 0.2 0.2 0.2 Initiator WPI-124 1 1 1 1 1 Curing conditions UV curing(UV irradiance) mJ/cm² 155 155 430 430 430 Thermal curing ° C. none none80 80 80 hr none none 2 2 2 Evaluations Hard coat layer thickness (□m)30 25 40 40 37 Haze (%) 0.62 0.75 0.8 0.75 0.96 Total luminoustransmittance (%) 91.87 91.87 91.81 91.91 92.23 Yellowness b* 0.86 0.790.82 0.86 0.6 Pencil hardness 6H 6H 8H 8H 9H

The abbreviations in Tables 4 and 5 refer to as follows:

EGVE: ethylene glycol monovinyl ether

CHXDM-VE: cyclohexanedimethanol monovinyl ether

TEG-VE: triethylene glycol monovinyl ether

DEG-VE: diethylene glycol monovinyl ether

HBVE: hydroxybutyl vinyl ether

IBVE: isobutyl vinyl ether

CHXDMDVE: cyclohexanedimethanol divinyl ether

DEGDVE: diethylene glycol divinyl ether

WPI-124: trade name WPI-124, supplied by Wako Pure Chemical Industries,Ltd., a 50% solution of a photoacid generator

As is indicated in Tables 4 and 5, the hard coat films according to thepresent invention (Examples 31 to 46) each had high surface hardness andexcellent transparency.

In particular, examples further using a vinyl ether compound incombination with the epoxy-containing polyorganosilsesquioxane ascationically curable compounds (e.g., Examples 33 to 41) gave hard coatfilms that had very high surface hardness even when irradiated with anultraviolet ray at a lower irradiance, as compared with examples usingno vinyl ether compound (e.g., Examples 31, 32, 42, and 43). Thisindicates that the combination use of a vinyl ether compound with thepolyorganosilsesquioxane both as cationically curable compounds allowshard coat films to be produced at a higher line speed, and thiscontributes to very excellent productivity.

Examples using a hydroxy-containing vinyl ether compound in combinationwith the polyorganosilsesquioxane as cationically curable compounds(e.g., Examples 34 to 38) gave hard coat films that had still highersurface hardness and still better resistance to thermal yellowing, ascompared with examples using a vinyl ether compound devoid of hydroxygroups in combination with the polyorganosilsesquioxane (e.g., Examples39 to 41).

The hard coat films prepared in Examples 31 to 46 were examined toevaluate the heat resistance (T_(d5)) and flexibility by the abovemethods and were each found to have excellent heat resistance with aT_(d5) of 380° C. or higher and to have excellent flexibility andprocessability with a diameter of 25 mm or less in the mandrel test at ahard coat layer thickness of 30 μm.

Example 47

Preparation of Composition for Adhesive

A composition for adhesive (adhesive composition) was prepared by mixingmaterials. The materials were 100 parts by weight of theepoxy-containing polyorganosilsesquioxane (S-1) (cationicallypolymerizable compound) prepared in Example 1, 50 parts by weight ofpropylene glycol monomethyl ether acetate, 0.1 part by weight of thetrade name San-Aid SI-150L (supplied by SANSHIN CHEMICAL INDUSTRY CO.,LTD., an antimony-containing sulfonium salt), and 0.005 part by weightof the trade name Auxiliary for San-Aid SI Series (supplied by SANSHINCHEMICAL INDUSTRY CO., LTD., (4-hydroxyphenyl)dimethylsulfoniummethylsulfite)).

Example 48

Formation of Adhesive Layer A silane coupling agent (trade name KBE403,supplied by Shin-Etsu Chemical Co., Ltd.) was applied onto one side of aglass plate (4 inches, supplied by SCHOTT Nippon K.K.) by spin coatingand heated at 100° C. for 15 minutes to form a silane coupling agentlayer. The adhesive composition prepared in Example 47 was furtherapplied thereonto by spin coating, then heated at 60° C. for 10 minutesto form a 5-μm thick adhesive layer, and yielded a glass plate withadhesive layer. This had a layer configuration including the glassplate, the silane coupling agent layer, and the adhesive layer disposedin this order.

Formation of Silane Coupling Agent Layer

A silane coupling agent (trade name KBE403, supplied by Shin-EtsuChemical Co., Ltd.) was applied to one side of a glass plate (4 inches,supplied by SCHOTT Nippon K.K.) by spin coating, heated at 100° C. for15 minutes to form a silane coupling agent layer, and yielded a glassplate with silane coupling agent layer. This had a layer configurationincluding the glass plate and the silane coupling agent layer disposedin this order.

Preparation of Bonded Article (Laminate)

The above-prepared glass plate with adhesive layer and theabove-prepared glass plate with silane coupling agent layer were appliedto each other with compression at a pressure of 200 g/cm² with heatingat 60° C. so that the adhesive layer of the former faced the silanecoupling agent layer of the latter. The resulting article was heated at150° C. for 30 minutes, and then further heated at 170° C. for 30minutes, and yielded a bonded article (laminate). The laminate had alayer configuration of the glass plate, the silane coupling agent layer,a cured product layer of adhesive composition (adhesive layer), thesilane coupling agent layer, and the glass plate disposed in this order.

The above-prepared adhesive composition and bonded article (laminate)were subjected to evaluations as follows.

Adhesion Evaluation

The adhesion of a coat layer (adhesive layer) derived from the adhesivecomposition prepared in Example 47 was evaluated by a cross-cut testaccording to JIS K 5400-8.5. Specifically, the glass plate with adhesivelayer prepared in Example 48 was heated at 150° C. for 30 minutes,further heated at 170° C. for 30 minutes, and yielded a sample. The coatlayer in the sample was a layer of the cured product of the adhesivecomposition prepared in Example 47.

As a result of the cross-cut test, no peeling of the coat layer from theglass plate was observed, and the coat layer was found to have excellentadhesion. The base glass plate herein had a layer configuration of theglass plate and the silane coupling agent layer disposed in this order.

Adhesiveness Evaluation

A razor blade was inserted into the adhesive interface of the bondedarticle (laminate) prepared in Example 48. As a result, no delaminationat the adhesive face occurred, and this demonstrated that the adhesivelayer in the bonded article had excellent adhesiveness.

INDUSTRIAL APPLICABILITY

The curable composition according to the present invention, i.e., thecurable composition containing the polyorganosilsesquioxane according tothe present invention, when cured, gives a cured product that offershigh surface hardness and good heat resistance, is highly flexible, hasexcellent processability, and offers excellent adhesiveness and adhesionto an adherend. Consequently, the curable composition according to thepresent invention is advantageously usable, in particular, as a hardcoat layer-forming curable composition and as an adhesive composition.

The invention claimed is:
 1. An adhesive layer comprising a curablecomposition comprising a polyorganosilsesquioxane, thepolyorganosilsesquioxane comprising: a constitutional unit representedby Formula (I); and a constitutional unit represented by Formula (II),in a mole ratio of the constitutional unit represented by Formula (I) tothe constitutional unit represented by Formula (II) of from 5 to 18, aconstitutional unit represented by Formula (2), thepolyorganosilsesquioxane having a total proportion of the constitutionalunit represented by Formula (I) and the constitutional unit representedby formula (II) of 95% to 99% by mole based on a total amount (100% bymole) of all siloxane constitutional units, the polyorganosilsesquioxanehaving a number-average molecular weight of 1100 to 2600 and amolecular-weight dispersity (weight-average: molecular weight tonumber-average molecular weight ratio) of 1.1 to 2.0, Formulae (I),(II), and (2) expressed as follows:[R^(a)SiO_(3/2)]  (I) wherein R^(a) is selected from: a grouprepresented by Formula (1a); a group represented by Formula (1d),Formulae (1a) and (1d) expressed as follows:

wherein R^(1a) represents an ethylene group,

wherein R^(1d) represents an ethylene group,[R^(b)SiO(OR^(c))]  (II) wherein R^(b) is selected from: a grouprepresented by Formula (1a); and a group represented by Formula (1d),Formulae (1a) and (1d) expressed as follows:

wherein R^(1a) represents an ethylene group,

wherein R^(1d) represents an ethylene group, and R^(c) is selected froma hydrogen atom and a C₁-C₄ alkyl group, and[R²SiO_(3/2)]  (2) wherein R² is an unsubstituted phenyl group.
 2. Theadhesive layer according to claim 1, the curable composition furthercomprising a curing catalyst.
 3. The adhesive layer according to claim2, wherein the curing catalyst comprises a cationic photoinitiator. 4.The adhesive layer according to claim 2, wherein the curing catalystcomprises a cationic thermal initiator.
 5. The adhesive layer accordingto claim 1, the curable composition further comprising a vinyl ethercompound.
 6. The adhesive layer according to claim 1, the curablecomposition further comprising a vinyl ether compound containing ahydroxy group in molecule.
 7. An adhesive sheet comprising: a substrate;and the adhesive layer according to claim 1 disposed on or over thesubstrate.
 8. The adhesive sheet according to claim 7, wherein thesubstrate is a semiconductor substrate.
 9. A laminate comprising threeor more layers, the three or more layers comprising: two adherendlayers; and an adhesive layer disposed between the two adherend layers,the adhesive layer being a layer of a cured product of the adhesivelayer according to claim
 1. 10. The laminate according to claim 9,wherein the adherend layer is a semiconductor substrate.
 11. A methodfor producing a laminate comprising three or more layers, the three ormore layers comprising two adherend layers and an adhesive layerdisposed between the two adherend layers, the method comprising thesteps of: forming the adhesive layer according to claim 1 on an adherendlayer; applying another adherend layer to the formed adhesive layer toobtain a resulting article; and subjecting the resulting article tolight irradiation and/or heating to cure the adhesive layer.